I started volunteering at 2 different hospitals (in different departments) to try and get a feel for how various hospitals and departments work -- and also to help people
. To my surprise, most of the staff (i.e. patient care techs, nurses, some doctors, etc.) thought that I was volunteering to try and get a job. I suppose that is a common thing?! I had no idea. But, volunteering is definitely a good way to meet some people that could share their experience(s) with you and even be a mentor for you. (I've met some really awesome people so far.)
I would try to go in to a volunteer position more to gain experience, than to try and secure a job for the future, BUT you never know what might happen!