There may be a few orphan books in the library folder. Move the library and see what is left behind.
Method 4.
Have your main calibre database on your main windows PC. And a full backup copy of the library on the NAS.
You can access the backup copy calibre library from other computers on your network. To avoid problems only update/add/delete/change books from the main PC. This setup means that you can access the main library from your main PC at the same time as someone else access the backup copy.
There are many sync-utilities that makes it easy to update the backup copy so it is identical to the main library. I use rsync.
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