I think at least the file paths will be different.
But the problems start already with access to the Plex data folder, which is by default not user-accessible on Android.
And even if you move this to an external disk drive (at least as I understand it), you always have to unplug this drive from the Shield and into a computer, where you then can manipulate the database etc. (like so: [HowTo] Plex database modification - Moving media the right/wrong way )
If your media collection is more than a few hundred items, I recommend you to avoid the Shield as a server. Use PC hardware.
