You have already guessed that it has something to do with flowers. By its etymology, a gathering of flowers, literary flowers. A florilegium, then, is an anthology, compendium, collection, miscellany, album of excerpts and extracts from writings of (usually) high quality by (usually) ancient authors. The Philokalia is a florilegium.
An album of pictures of flowers would also count as a florilegium, and, I suppose a book of actual dried flowers would as well.
The plural is florilegia.
UPDATE (10/15): Patrick Kurp of Anecdotal Evidence informs me of an entry of his, one rather more erudite than mine, on the topic. He also points out that some weblogs count as florilegia, Gilleland's for example.
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