One thing to note - even if books AREN'T in Calibre's database, Calibre can still modify the metadata in a limited way; it can edit the "Tag" (Categories), the title of the document, or the author field. If you want to modify anything else, that'll involve importing it into Calibre again.
Just a nice, simple GUI-based way to modify the title shown on the reader (when the metadata shows something other than the file name).
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