Some good points in this thread. I'd vote for...
- Avengers. The first in-universe crossover event of its kind, and it's changed the industry. Everyone is still trying to do Avengers. DCEU, Dark Universe, Netflix's Defenders, Sony's Marvel universe - everyone still wants their own Avengers, 8 years later, but the MCU has been the only real success so far, both critically and financially.
- Winter Soldier. I think this film was important for three big reasons.
1) It was the first solo film to not exist in its own isolated bubble. Sure, Iron Man 3 chronicled some repercussions from Avengers, but not
really. IM3 and Thor 2 were more of the same. Winter Soldier, the world felt connected for the first time. It made sense that Black Widow, Nick Fury and Maria Hill would be around.
2) It was the first MCU genre film, essentially. This started a trend where each film had a pretty distinct style, which has probably prolonged the life expectancy of the genre. Filmmakers have expected superhero films to go the way of the western for years, but when one film is a spy thriller, and the next is a space western, and the next is a heist film, and the next is a coming-of-age high school film, they tend to stand on their own more.
3) This film deviated from the age-old formula of "do it again, but here's a new villain." Successful superhero films were quickly followed up by the announcement of a sequel, and with the tease of "this time he fights Doc Ock." "This time they'll fight Ultron." "This one will have the Joker." Usually the sense of normalcy is shattered by a new villain, usually acting alone, who arrives and stirs things up. And usually it's back to the status quo after. But in Winter Soldier, the villain was Shield - previously a force for good - which had become corrupt. And instead of killing the main antagonist (Bucky), Cap had to try and redeem him. It wasn't a fight that could be won by using superpowers.
I think Iron Man 1 set the tone for phase 1, but Winter Soldier set the tone for everything that came since, and Avengers has set the tone for a lot of the blockbuster film industry. But that's just my two cents!