You never know whom you may meet and where you may encounter them. The woman in front of you at the dry cleaners may be the owner of that hot boutique that just opened down the road. There are a number of volunteer opportunities. Hospitals, animal shelters, local charities, nursing homes and special events are a good place to start. Much like volunteering, internships are experience-building opportunities.
Many companies utilize internship programs.
For information, check with your school Career Guidance Center or the company's Human Resource department. Don't take underwater basket weaving if you're interested in becoming a chef. It's also good to talk to people that have your dream job. Find out how they got started. Try to learn the good and bad points to the job.