The 'Daredevil' moment in Ace Combat 7 is obviously incredible but I'll go with 'Two Pairs' from the same game instead. You're thrown into your first dogfight against Mihaly, weaving between tight canyon rock structures and avoiding lightning strikes, desperately trying to connect with a missile, all while the radio chatter in the background glorifies your abilities to an absurd degree. The power fantasy aspect of Ace Combat is so over-the-top but it completely works.
'Merchants of Novigrad' happened to be the first track that played on my initial visit to the city of the same name in The Witcher 3: Wild Hunt, and it perfectly captured the hustle and bustle after spending tens of hours wading through the oppressive bogs of Velen. I loved the game already but I think wandering the streets and soaking in the atmosphere that first time was the moment I knew I was playing a new all-time favourite.
This track would periodically play during gameplay in Freedom Fighters and it seriously pumped me up for some action every time without fail. Even when trying to play conservatively, I was compelled to go guns blazing with my squad when it played. It's perfect for a rebellion.
Rescuing Sean to this music in Red Dead Redemption 2 was another one of those moments that brought me totally onboard for the adventure, if only to experience the entire soundtrack. It's such a shame this one doesn't appear on the official release of the score.