I honestly hadn't really made this comparison before, so I'm not sure how things ultimately stack up when all tallied together. I'm definitely interested to try it out, though:
TV
Agent Carter - Whitney Frost is definitely a +1, but I have to -1 as well since the season 1 villain(s?) were so forgettable I literally can't remember who they were.
Agents of Shield - Grant Ward +1, Aida +2, Radcliffe +1, The Superior -1, Hive -2
Daredevil - Kingpin +3, Madame Gao +2
Jessica Jones - Killgrave +3, Alisa +1
Luke Cage - Cottonmouth +2, Mariah +1, Shades +1, Diamondback -2, Bushmaster +2
Iron Fist - Harold Meachum +1, Bakuto +1
The Punisher - Billy Russo +1
Defenders - Elektra +1, Alexandra -1
I haven't yet seen Inhumans, Runaways, Cloak and Dagger or AoS season 5 (any villains that seem 'missing' would've scored 0, ie, neutral), so the total score for tv is: 17
Movies
Iron Man - Stane 0
Iron Man 2 - Whiplash -1, Hammer -1
Iron Man 3 - Mandarin -3
Incredible Hulk - Ross +1, Abomination -1
Thor - Loki +3
Thor 2 - Malekith -2
Thor 3 - Hela +1, Grandmaster +1
Captain America TFA - Red Skull +1
Captain America TWS - Pierce +2, Arnim Zola +1
Captain America CW - Zemo +3
Avengers Age of Ultron - Ultron +1
Avengers Infinity War - Thanos +3, Ebony Maw +1
Guardians Vol 1 - Ronan -2, Nebula +2
Guardians Vol 2 - Ego +2
Ant-man - Yellowjacket +1
Dr. Strange - Kaecilius -1
Spider-man Homecoming - Vulture +3
Black Panther - Killmonger +2
So the movies total is: 17
Pretty even overall, then, although I have actually seen all the movies and not seen all the shows. No idea if the missing shows would tip the scales towards tv or away from it, though.