Plex combined the same show that is in two different libraries

It shows that option whenever a show has been combined with items from different folders.
Which means if you click that, it will separate the show into two items.
One with the files from /TV Shows DVR and one with the items from /TV Shows.
It’d be interesting to see in which library the two show posters will end up.

I’d try the Plex Dance with each of the show’s instances.
Dance one at a time, not both together.

How this came about I can only speculate:
Do you have automatic or periodic library scanning activated?
Was the folder /TV Shows DVR previously named /TV Shows? (even if only for a few seconds)
The two version might have gotten entangled when a library scan coincided with you working on your file and folder organization.
And now it is difficult to disentagle them, because technically the files are all there and present. So the server won’t remove them upon a library scan.

I can only recommend you to disable automatic and periodic library scans while working on your media files. Whether you do adding, removing, moving, renaming or anything else to your media files.
Make sure that the server will only scan the files when you are finished with your work.