The downside of jumping right into the startup game right from school is that your lack of experience in business, networking, fundraising, managing relationships and delivery is going to work against you right away unless your first startup job is with experienced entrepreneurs who will work to bring you up to speed in relation to technology (or biz dev if that's your (current) calling) and teach you everything they know about the business, not just the current business conventions that guide it. Being able to learn the business and identify opportunities is key; until you're able to do that you're just writing aimless code or making cold calls in the hopes of some modicum of success.

I'm not so sure that large companies can, or will provide the type of opportunities that a person who's interests lie in discovery will need in order to find balance in work and life.