Beware of the 'hide file extensions' issue. By default, windows will show you the file name without the extension. What this means is that a file with the visible name 'metadata' could have the real name 'metadata.db'. If you rename it to 'metadata.db', then its name will really be 'metadata.db.db', which calibre won't be able to find.
With the option turned on (as I said, the default), you should see the name 'metadata' with type 'Data base file'.
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