Are you asking if there is a way to use CC's cloud connection to see books in your calibre library that are not in CC? If so then the answer is yes. Use CC Cloud to connect to Dropbox, tap on the "On Device" category, then "No". You will see all the books that are not in CC. Tap the menu button (the three dots) and choose "Download all".
Note that this is also easy to do using the wireless device connection. Connect CC to calibre, search for ondevice:false, select all the books the search finds, then click Send to device. The wireless device connection also automatically updates all the metadata for the books in CC, and can (optionally) ask calibre to send any books that have changed since the last time you connected.
If you are asking something else then I need more explanation.
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