This knowledge base answer on steam's support pages seems to answer your question, or at least part of your concerns. The important bit is
The accounts will share the core files for any games the accounts have in common, but each account will maintain its own custom content and configuration files.
This sounds great if that "custom content" includes saved games.
You could also try the new family sharing support, but it is in beta and you'd have to sign up for it.
This forum seems to indicate that the games would be installed only once, but each user would have their own save files. Although, I think this depends on the game.
I did this just tonight (Xbox 360 version, for what that's worth).
Maria does get a super speed boost at the beginning of the race, but if you floor it and manage to keep from hitting the sides of the track, you will eventually catch up with her. I don't know if she corners poorly or if her top speed is less than yours, but she doesn't maintain her early lead throughout.
The steering and the camera are the major problems here. You will generally want to make frequent/rapid small adjustments rather than really throwing the stick to one side or the other. If you do that, you'll tend to make an overly tight turn suddenly and hit the side of the track. It takes a few practice runs to get the hang of the curves - the camera tends to fail to keep up with these, so you won't have a clear idea as to where you're going until a few seconds after you turn.
If you can stay on track, you can catch up - I tended to pass her or bump into her between the last checkpoint and the finish line, generally speaking.
An Alternate (Cheesy) Method
I discovered after some races with Ghost Rider that sometimes he got off-track and took forever to finish the race. Some further investigation shows that the AI actually drives the course "legally" - their time changes depending on what kind of traffic and so forth they encounter.
So, what good is this information? Just park something in front of NPCs you intend to race. They can't quite figure out how to get around it, and will give you a commanding lead while they work it out.
In this specific instance, Maria Hill is on an elevated track. If you jump down to the vehicle call-in point and summon a helicopter, you can land it on the track in front of her with a bit of effort. As much as possible, try to keep your side of the track clear. Then, when you start the race, she'll run into it and give you an advantage.
This is obviously much, much easier on the ground, but it is doable on her track. I used this trick on the second race with her to great effect.
I'm out of these races now, but I do wonder what would happen if you parked a big character (ie, the Hulk) as your co-op partner in front of her....
Best Answer
I had wondered why I was seeing reports of the game being buggy while I was searching for an answer to this, now I know why.
Space then Numpad 5 is the proper key combination to use for skipping the intro based on my key configuration, but so far it has only worked twice out of around 30 launches.
Also as far as I can tell there is no file to replace/delete that would allow me to skip the game (at least not in the Steam version), so I will have to live with skipping the intro on the rare occasion that the game allows me, and otherwise wait it out.