I started working with startups 20 years ago in grad school and have never looked back - starting up 4 different companies. I did work for a big company part way through my career for a year between startups and couldn't wait to get back into the startup world. You'll learn so much by going ahead with your passion and starting up a business. Although, you do need to be practical. If you have a family to support at this time, then that needs to be considered.

You can always bring on a partner with big company experience if you feel you need it on your team. The challenge I always see from those who desire to start up a company but end up in a big company is that it's harder to leave that big company the longer you're there.

In the end, follow your heart ... and good luck!