View to an Entrepreneur-Volunteer
Getting someone to give you the chance to learn something new, or prove yourself in a given field can be quite a challenge. The marketplace is competitive and taking a chance on someone who isn't showing their experience in a given field is more than most employers are willing to extend to a newcomer.
Volunteering is a great way to get your chops in a new field or to develop that new skill set. You may already have a degree in that area, but without "real world" experience possible employers may not give you the time of day.
Perhaps you may want to work for an employment agency or in HR. A possible connection would be any position where you are interviewing people, managing people or being a "group leader". In the business world, managing other people really puts you further up the ladder and takes you from the front desk or back office. In a non-profit, managing other volunteers is often a position you are find yourself in if you've been somewhere longer than 6 months.
This doesn't just apply to working onsite with a non-profit. If you are looking for work in website development, you probably already know that offering your skills up for free or small bucks to the kind of future clients you'd like will give you the portfolio of work to help you win those clients in the future.
It may take a while to find the perfect volunteering match, but take it from someone who's entire business was influenced by ONE volunteering experience 15 years ago, everything we do can be a learning experience. Go for it. Try some new skills of for size and help others on the way.
Some resources (not personally vetted by me)
Volunteers of America
Idealist/Action Without Borders