The phrase to play on a device should be “on the”, there would be too many false positives if it was just “on”.
I haven’t built in any stop, pause, next, etc commands yet as you can usually just say “hey google stop”, “hey google pause”, etc. without having to say “tell plex”. I do plan to build those in at some point.
There is also a built in method that avoids a bug with plex where it can cause a blank screen. The fix for it is to essentially tell it to play the item multiple times. This can make it so if you tell something to play and then immediately tell it to stop it will play again, but if you wait a second or 2 after starting a show before telling it to stop then it will stop just fine.