You can make new collections from the same place you add games to collections: from the Add To Collection button in the upper right corner of each game page. As for your library, it's available from your account menu, at the right end of the site toolbar. Hope this helps.
Yes, you can. The library includes collections, and things you've rated. If by library you mean things you own, you'll have to pay something for a game before it shows up there. That's only fair.
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