this may be my last idea but if you have not done it already...
whenever an app misbehaves I will go to settings -> apps and force stop, clear cache, and retry
if no joy I will add clear data, so force stop, clear cache, clear data, then retry ( clear data will mean you have to reconfigure all the app settings so if the app has its own backup preferences, maybe do that first - but here were are testing if its the app preferences that are somehow messed up, so maybe not)
it should not be necessary to also power cycle the device but add that to the mix for the ultimate clean
after that its going to be a case of work with developer, use debug mode, send logs etc when instructed
I think you said that you have no 2nd device to test with, but you could optionally open up internet access to your calibre library, share the access credentials with app developer & let them try to reproduce your issue in the app on their own devices
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