I've been on both sides of volunteering. When I was on disability I started getting back into the world by volunteering. I volunteered at my local library. They were thrilled to have me and I got to do something real. After I had volunteered for a while they offered me a part time (10 hour/week) job as the children's librarian. Eventually, I went back to school to become a librarian.

Now I have volunteers who come to help me. I love them because I get stuff done that wouldn't happen any other way. I'm always careful to make sure that they know how appreciated they are. I give them meaningful things to do and make sure that they know how important it is for those tasks to get done. I am willing to teach them things because they are doing free work for me. I know I have to make it worth their time.

If your current major "job" is finding a real job, then you might as well volunteer while you are looking. Then you have something to write on your resume, and someone who will give you a reference. It is something productive that you can do while you are job hunting.