As I said, you can access metadata for books that have already been downloaded. If I were you I would download my entire calibre library to CC and be done with it. This is especially true given that we are talking about 1% of the books.
I understand that you are saying that you don't want to use calibre's mail-to-amazon function because the books will end up as personal documents and not as books. In any event, CC wouldn't be involved here.
I understand that you are saying that you want to access the metadata in a calibre library for books not on your device while either or both of the fire and the content server are offline. CC cannot do this. CC can access metadata for books in your calibre library but not on your device only if your Fire and either a calibre content server or a calibre GUI instance (wireless device) are online. There is no way for CC to store a calibre library's metadata offline without storing the books as well.
My take: the conditions you have set make CC not the right product for you. I would offer a refund but Amazon makes that very hard to do. My apologies.
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