I am curious why that file exists if it can't be used as the OP desires? (Recover Library Items from Device)
That (xml) file is HUGE, bigger than metadata.db for a smaller count of books. AFAIK, it exists just to put the initial On Device tick marks in the main library.
Metadata writing on Save/Send, to PDF is not happening per Kovid, so the user is stuck with the original (lame?) metadata.
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