Hmmmm
Shatner/Kirk: Hands down TWOK - "Khaaaaaan"
Nimoy/Spock: TMP - reporting for duty and letting the tiniest emotion show when he boards
Kelley/McCoy: TFF - Just knowing the actor's personal struggle with the euthanasia scene
Doohan/Scotty: TFF - for not killing the Shat for the shit that Shat put Scotty through.
Nichols/Uhura: TSFS - "This isn't reality...It's FANTASY!"
Koenig/Checkov- TWOK - "botany bay..botany bay...BOTANY BAY...DAMN!!"
Takei/Sulu- Hands down "Don't Call Me Tiny!"
Larroquette/Maltz: TSFS "I do not deserve to live!"
Lloyd/Kruge: TSFS: The "Share this with no one" speech.
Hicks/Taylor: TVH:Just for going Bra-less most of the movie!
Shuck/Klingon Ambassador: TVH: Best Klingon Speech Ever!
TNG
Stewart/Picard: FC - Hands Down "The line must be drawn HEEEYAHR!! NO FURTHER!"
Frakes/Riker: I - For believing he could make us believe that an old computer joystick with a long shaft, that rises out of the floor no less, could control the Big E's flight.
Spiner/Data: N - For believing he could make us believe that his best option was to jump through a hole in the ship, fly out into space and land on the bad guys ship's hull to gain entry. (what? no transporters on all those shuttles?)
Dorn/Worf: FC - "Assimilate This!"
McFadden/Crusher: G - getting shoved off deck into the water. (pretty much the only acting she had to do ... well maybe FC when she ordered Holo-Doc to delay the Borg)
and speaking of ....
Picardo/Holo-Doc: FC - "...maybe I can recommend some analgesic cream?"
Burton/Geordi: I - It was touching to see him use his real eyes to see a sunrise...or am I a sap?
Sirtis/Troi: FC - That "drunk in the bar" scene
Wheaton/Crusher: N - the only flick he was in and mostly cut from
Barret-Roddenberry/Computer: Her best work Hands Down was in FC with the whole self destruct scene. It was gripping!
Mulgrew/Janeway: Intense communication scene with Picard...gives me goosebumps!
That's all I can think of right off the top of my head!
Oh Wait Anthony Zerbe in I- simply for helping pull off the single most gory scene in a Trek film ever.
Okay, now I'm done....