What's the easiest way to migrate from a Linux server (Raspberry Pi4) to an Nvidia shield server?

There is no easy way as such. You’ll still end up downloading/refreshing metadata again for many/most items.

Try it this way:
Set up the server on the Shield.
Move the data folder to an external drive.
Set the preferences to update the library automatically or regularly to ‘Disabled’.
Disable also “Empty trash automatically after every scan”.

Make sure you can access this drive and can identify the Plex data folder on it.
Copy the contents of the Plex data folder on the Pi to the external drive.
Make sure that the Plex server on the Pi is not running while doing so.
EXEMPT the file Preferences.xml from copying.

If the server is starting at all on the Shield after this, edit each library first and point it to the media shares. (I’m not even sure if you can mount cloud storage on the Shield).

^^^ The above is pure theory. Normally, moving a server to a different operating system is not supported at all.
I’d be interested to know the results you get.