Someway to test MCEBuddy2x before unleashing it on my entire Plex video library?

Welcome to the community. You’re on the right track. Also check out this topic and the Plex section for more tips: Plex - MCEBuddy

To answer your question about testing it, just redirect the output directory in the Conversion Task settings to a different folder and see how it works out. If you’re happy set it back to the original setting you had.