Volunteering works to add experience whether you are new to the field or have been out there so long you feel fossilized.  Another tactic that others have mentioned but I'm going to bring up again is the ability to turn your prior experience into an asset.

My volunteer work includes child advocacy organizations, neighborhood associations, community health organizations, arts organizations (informal - as an artist), museum associations, museums - as ones I can recall right off.  Some of these I did while a student, some I did while looking for work, some I did while gainfully employed.  If your present position keeps you from experience that you think is valuable, you can find a way to gain that experience through volunteering.

I've worked as a clerical office worker, project manager, non-degreed librarian, typist, museum director, curator, registrar, cleaning woman. (The last four positions sometimes combined themselves and were usually formally lumped into the title "Museum Director!" The stint I did with an after-school art program taught me a lot about maintaining children's attention. One of the clerical positions was in a start-up government agency where everything was more than full speed, we all wore many hats, most of us were underpaid, and the agency was a political hot potato. In retrospect, it was perfect training for work in small museums!

My most enjoyable jobs were project oriented. They were focused, people were grateful, I felt productive and appreciated.  The appreciation and focus has never seemed as great in other places. 

I never got a job for someone I volunteered with but I've certainly been a stronger candidate for other jobs from that experience. 

As an aside, I do sympathize with those that lack the time to volunteer. For years I was in that boat. In those years I never would have dreamt that there would be a time when I would use vacation time and pay my own transportation and lodging to volunteer.  In the meantime, when you have very little time to volunteer, look for what you can learn on whatever job you have.

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