We may think we know all there is to know about the Burrell Collection, which has been on display in its stunning purpose-built A-listed museum in Glasgow's Pollok Park since 1983.

After all, we've had 30 years to bask in the reflected glory of the shipping magnate Sir William Burrell's astonishing range of artworks, from medieval stained glass and tapestries, oak furniture, weapons and armour to Islamic art, artefacts from ancient Egypt and China, and modern sculpture, gifted to the city in 1944.

But it's the collector's cache of 19th-century French Impressionist oil paintings and pastels, much of which has not been seen by the public, that has been exercising the artistic antennae of curator Vivien Hamilton for the past year to the extent that she is seeing the works with fresh eyes.

Although an expert in her field – she is published on such subjects as Joseph Crawhall, Boudin and French Painting from Kelvingrove Art Gallery – Hamilton can barely curb her enthusiam for the items she is currently preparing for Glasgow's somewhat unassuming retrospective. And it's catching.

"Even though I'm an expert, I only know such a tiny amount, and every time I open a book or read an artist's letter I notice something completely new and different," she says. "What I love best about many of these Burrell works are the stories behind them, and the links between the people involved."

The 33 works on show (of the 650 paintings, oils and watercolours at the Burrell, there are 200 19th-century French works, though not all of them are Impressionist) include such rarities as Fantin-Latour's delightful Chrysanthemums and Spring Flowers; Le Sidaner's haunting The Madonna Of Bruges, Rocky Inlets By Moonlight and The Lighted Window; Jongkind's Fabrique de Cuirs Forts; Sisley pastels Peasant Woman With Cows In A Meadow and Landscape With A Donkey; and two Manet pastels Women Drinking Beer, and A Cafe On The Place de Theatre-Francais.

Degas's Portrait Of Edmond Duranty is one of Hamilton's favourites, and although it's very often on the cover of exhibition catalogues and posters, stories are still being added to this day.

"Duranty was a writer, artist, poet who wrote different papers, novels and plays. He was a close friend of many of the Impressionists, especially Manet. In 1876 he wrote a pamphlet entitled The New Painting. He didn't call them Impressionists, but described a new way of painting among this group. They used guache, watercolour, pastels, and depicted modern life, not the past. They showed people as they were, so their character comes through. People accused Degas of having written it as a piece of self-publicity, but it was actually Duranty who wrote it.

"Depicting Duranty with his hand on his face is really powerful," she adds. "He died very suddenly soon after sitting for Degas. A visitor to the Burrell from Oxford, a retired oncologist, emailed me recently to say he wondered if Duranty could have had lung cancer. He reckoned Duranty might have been suffering from a drooping eyelid, or Horner Syndrome, which is a symptom of the disease. This is something I really want to pursue."

Another way of looking at this is that Duranty might have been depressed; so Degas was depicting him exactly the way he was as an example of true Realism.

"I love the idea of how close the artists were. Manet was also a pal of Duranty and Degas, and he once objected to something that Duranty said in a review of his work that he challenged him to a dual in which Degas got stabbed. He always said it was because his shoes were too big for him to move swiftly, rather than because he was a bad swordsman."

The relatively unknown Henri le Sidaner, who was influenced by Monet but became more interested in the atmospheric melancholy of twilight, remains an enigma. He showed an exhibition in Glasgow in 1903 and it was advertised in the local newspapers, but there is no catalogue. The curator has been in touch with the artist's grandson but so far it appears no copy of the catalogue exists. There are three Le Sidaners in the Burrell Collection, purchased in 1917 and 1919, that will be on show.

Burrell also purchased two huge paintings by Lucien Simon; it was unusual for him to buy such large canvases, but the subject matter of Brittany fairgrounds and racecourses was typically realistic. These are undated but Hamilton reckons they are late 1890s or early 1900s.

"What was he doing buying these?" she wonders. "We just don't know. But I wanted to show them because they have not been seen before."

Meanwhile, and behind the scenes yet further, stories have been emerging through the restoration of some of the Impressionist works at the Glasgow Museums Resource Centre in Nitshill. Senior curator (art group) Polly Smith has carefully removed the yellowed, century-old natural resin varnish used by Le Sidaner on his Snow, 1901 – the material used by artists and restorers at the time. Once removed, it is replaced by synthetic resin varnishes which age slowly and well.

"It's very exciting to see this painting in its original form for the first time since it was unveiled 1901," she says. "I feel we're revitalising and enhancing the artist's work. The passage of time can be good for a painting, but removing the obscuring part of it also informs us of the intention of artist."

Hamilton has also selected a small exhibition of Burrell-collected 19th-century works that are not Impressionist but which were painted by artists who were living at the same time. Stunning, but previously unseen, works by Ribot, Monticello and Bonvin, all "independent" artists, will be hung in the upstairs gallery.

Ribot's The Studious Servant, for example, "sings out of the canvas", says Hamilton. "His use of light is very important, as it was to the Impresionists, and his style shows the influence of Vermeer and Rembrandt though interpreted in a different way from Manet. His use of hands and the face, and the perspective that something is happening in a room and looking through to another room, is typical of the Realists. Bonvin was also a realist and Monticello was a contemporary of Van Gogh, who loved him best in the whole world for his colour and texture."

She says she was "shocked" that the public had never seen this part of the Burrell Collection. So, what does this say about William Burrell? "I'd love to know what William Burrell knew. Was he aware of those links between the aritsts? I'm trying to work that out by looking at what Burrell bought, where from and when.

"He could have bought Monet but he didn't. But he did buy Boudin, who painted his life of ships and water, seen in the Jetty At Trouville and The Empress Eugenie. The French weren't buying him but the Scots and the Americans were. Was that just because they were cheaper, or because he really loved them?"

Hamilton adds that when she joined the Burrell in 1987, it was "mobbed", especially at weekends. "We're very guilty of taking things for granted," she says.

"People hadn't realised how much Sir William had on their doorstep and were gobsmacked. We used to rotate the collection until the mid-1990s, when resources no longer made that possible. So people got used to the permanent display and just didn't come back.

"I'm still awed by what Burrell was able to achieve. He did have an eye for quality and I think he loved colour and I think he loved texture. The frustrating thing is he didn't leave anything behind – from his letters we get an idea of him, but we don't really know the person who was doing this. I'd love to know what he thought about what he was doing, and why, and what he loved best. Was it the pastels?"

There is one thing we do know beyond question.

"He cared about the public and he did put his stuff out on display," notes Hamilton. "It's not like he wanted to keep it personally for himself."

Burrell's Masters of Impressionism runs from July 4-January 5