I don't know what genre of books you like, but I mainly use the Sony Site, and also BooksOnBoard. I think I downloaded one free book from Fictionwise...but I try to stay away from them because their selection is limited. I also got several romance books FREE from Eharlequin. If you go to the wiki page on this website, there is a list of stores.
As for Calibre, I haven't used it so I don't have any helpful tips there.
Enjoy your reader. Mine is pretty new too and I LOVE IT!!
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