Plexamp Fails to Load as Startup Service

which user should execute this service? As far as I can see, service config contain user PI which is not existing on DietPi. But I guess you tried to change to user root?

Home directory of user root is not /home/root/, it should be /root/ only

BTW: the strange permission of your files are coming from the archive you download. There the owner runner and group docker are defined.

I recommend to change to the user who should run the service.

BTW: Plex (if already installed) has an own user called plex

PlexMediaServer install:
PlexMediaServer install: Now installing based on:
PlexMediaServer install:   Installation Type:   New
PlexMediaServer install:   Process Control:     systemd
PlexMediaServer install:   Plex User:           plex
PlexMediaServer install:   Plex Group:          plex

Maybe you can use this one to run your script/service.

root@DietPiR6S:~# cat /etc/passwd | grep plex
plex:x:997:1000::/var/lib/plexmediaserver:/usr/sbin/nologin
root@DietPiR6S:~#
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