Are you aware of the option to configure Plex to use the DVD order?
You can Edit the Advanced Settings for the show, and change the Episode ordering from Aired to DVD.
That’s appropriate if your filenames match the DVD ordering.
I think this has some data management issues, but I really like this idea from a UX perspective.
I don’t think this metadata is available in a way that would be reliable for Plex. User-provided files don’t have reliable durations/intros/commercials/framerates/skew.
My favorite solution is to split the episodes apart, using MKVToolNix. It’s not the easiest but it has the best overall results.