One easy way to avoid any problems is to not share the "live" library, but a local backup copy instead.
You can write a script that automatically makes a backup copy of the library every time you exit calibre, just modify the script that starts calibre, or create a new one. If the backup is done using a sync utility to a local filesystem, the backup copy can be updated in a few seconds, and will hardly be noticed. And the backup copy can then be shared safely and freely over the network.
The remote computer should do this in reverse. Update a local copy of the calibre library from the shared backup copy of the other computer. This can be done using a script that both update the local library from the shared copy, and starts calibre. You might even be able to add some tests so the script only attempts to update the local copy if the shared backup copy is available. That way you ensure that you automatically have the most resent copy of the library on the remote computer.
This means that the library is safely and efficiently replicated from the first main computer. It also means that any modifications made on the second computer will be lost.
I don't use Windows, so I can't suggest how you should write these scripts. But if you google "check if network folder exists windows batch" you should get some ideas. Likewise there are plenty of sync utilities.
I use rsync in Linux to automatically make a backup of my calibre libraries every time I exit calibre. Rsync makes it possible to make full backups, but link to an earlier copy of the files that haven't changed, instead of copying them. So it provides what looks like separate new full backups at almost the same speed as a sync utility can update a single backup copy.
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