I must say that once you get on a path and start doing well, it's harder to change course. So think long and hard about what you want to do before you take any old job. If you get an offer that sounds exciting, though, go for it. You've mentioned how important it is to build relationships with people in your industry and how this has helped further your career. It never hurts to take someone to lunch and ask them questions about their career paths.
People generally like to give advice.
If you're just starting out, send a note. Follow up with a phone call, and ask them if they have time for an informational interview. When you meet with someone, know your stuff, but don't pretend to know more than you do. It's better to ask questions than to sound silly. After a meeting, send a thank you note.