Unrequested commentary - whatever your motivation for separating Work and Personal, this would effectively undo that. Personally I think it’s a valuable separation, and if you can possibly do so, I would encourage you to keep them separated.
You would need to install Plex in both environments.
They would be independent Plex server installations, sharing a Plex data directory, sharing access to media.
To make this work, it would be important that the media be accessible over identical drive letters in each environment, or from the same network paths.
You would move the Plex data directory to a location accessible by both environments. Library configuration is stored in the data directory, and would be shared between the instances.
[HowTo] An extended guide on how to move the Plex data folder on Windows
It would be important to update the Plex Media Server consistently in each environment. Many settings would be stored in the registry, and changes would need to be made in both environments.
If you felt like being clever, you could consider initially cloning the Plex registry keys between instances. Both instances could use the same Server ID, and there would be just one server listed on your account. The big advantage of that is that your client/player devices would just see one server ID, and wouldn’t need to switch back and forth to play things.
