1. DS9
2. TNG
3. Voyager/ Enterprise
4. TOS
for me, DS9 have the most complex characters, best acting and probably the best action scenes of all series. I was actually in love with Kira when I was younger
TNG has Picard of course and it's pretty much on the same level as DS9, but I always felt that series never started something big like Dominion war (or like journey home in Voyager).
Voyager on the other hand has unique setting, but the worst captain imo. I just couldn't take Janeway seriously. characters in general aren't as complex and interesting as those in TNG and DS9, so...
Enterprise isn't much better in that regard, but it's pretty short so that never really becomes an issue. and yes, T'Pol
TOS is simply ridiculous unless you grew up watching Spock and Kirk. it just lacks quality when you put nostalgia aside.
as for movies, Voyage Home (1986), Undiscovered Country (1991), Star Trek (2009) and First Contact (1996) are the ones I probably loved the most.