I have also set up the Dropbox implementation today, and noticed that the metadata.db file does NOT sync to Dropbox until you close Calibre (close, not just minimize to the system tray).
Assuming the metadata.db file is synced correctly, then when you open Calibre on another computer, it should be using the latest version of the database.
Best practice: Open Calibre only to add files/metadata, then close it afterward. That way you won't get any database inconsistencies. If you try to access it from two places at the same time, "bad things" will happen.
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