Yeah it's Paris and it's not even close. He was the first test pilot to break the trans-warp barrier. Smashin hot Klingon ass, and banged his captain when they were lizards. Mans a fuckin Starfleet legend.
I'd say Lt Mayweather as runner up. Dude was a freighter pilot and they basically tossed him in our very first combat spaceship that can hop around the galaxy. And was like "I dunno figure it out as we go" lmao.
Ortegas and Paris are definitely the most pilot like pilots character wise though. Both of them have fighter pilot personalities, excited to get into the action and do wild shit.