Do you want to transfer the Database? Or your files? Those are 2 different things…
If you want to transfer your files to the larger drive follow these steps:
Copy Hard Drive A to New Hard Drive B
Once the copy is complete, shut down Plex
Change the Drive Letter of Hard Drive A to something else
Change the Drive Letter of Hard Drive B to what Hard Drive A used to be
Start Plex.
If you want to transfer the Database, then you need to follow this: