That is a good question. It got me thinking. I would say no.
The Marvel Cinematic Universe idea encapsulates the entire concept of Marvel Comics. Historically, Spider-Man is a character seen center stage of huge Marvel stories. The Infinity Gauntlet is a prime example, but that is not generally the case. His personal story is mainly not only Earth-bound, but New York City-centric.
I would want a character or characters that would allow the franchise to grow organically towards cosmic level stage as the real MCU did. That said, I would not have started with Tony Stark
IF I had access to all character intellectual/production rights. It makes perfect sense how the actual MCU started with Iron Man, who was a core member of The Avengers.
Me? My choice would not be a populist one, but it would have held true to the publisher's books from the Silver Age:
The Fantastic Four
My first four MCU movies: a) origin, b) Namor The Sub-Mariner, c) Galactus Part 1, d) Galactus Part 2.
Bam. Earth-to-cosmic right off the bat. Then I would slowly start layering the franchise with everyone else. The Man of Iron. Thunder god. The hero. The gamma bomb tragedy. Avengers. The uncannies. THEN I introduce Peter Parker, probably within the X-Men story before debuting in his own movie.
Just my nerdy alternate universe take, lol.
Edit: Somehow forgot The Incredible Hulk.