Go ahead and volunteer, but don't plan on being hired by the place you volunteer at. I work for a nonprofit and we had a long time volunteer. He eventually was hired for the position he had been volunteering for, but when an opening came, they didn't go for him because they didn't want to have to pay him more than someone new off the streets. If you can volunteer for a couple months somewhere to brush up on your skills and connections, and then move on, that'd be a good starting point.