Mod Podge is only a sealant for the foam so you can paint it with whatever you want without the foam potentially degrading or reacting with aerosols in spray paint. You can also use white glue (like Elmers) or plain old wood glue to seal your foam.
If you use an enamel paint and a clear coat on top of either white glue, wood glue, or Mod Podge, it will be just as weather resistant as your car. However, anything you accidentally smash against is probably going to crack and/or chip it (door frames, table edges, unruly children, etc...). Acrylic will be a bit more forgiving when you over-flex it, but it's water soluble. Even the best clear coat won't guarantee it won't get ruined in a wet environment.
If you're sure you're going to be stuck in rainy or wet environments, you're better off using several coats of Plasti-dip as your sealant on the raw foam parts, then paint with automotive grade paint and a clear top coat.
IMO, Plasti-dip is a decent undercoating, but personally I don't like using it and for a full suit of armor. And it can get pretty pricey compared to glue depending on the quality of your foam and how porous it is.
My advice...Seal your foam with a heat gun first, then cover the whole thing with 3 coats of wood glue (it creates a harder shell than white glue, it's better at filling gaps, and if you buy a decent quality product, you can even sand down high spots), then paint with an enamel spray paint, then seal it all with two layers of a satin finish clear coat.
The Marvel section in the costuming forum is a wealth of info on this subject. Read through several of the Iron Man threads there and you'll get a much better understanding on what works and what doesn't.