Depending on the volunteer work, you can defer student loans, and some other loans, not sure on the type. As for employer recognition and value, it greatly depends upon the employer.
Volunteer work would look very good on a resume if you were applying for a social service position or working for a charity organization. If you were applying for a computer programming degree, it wouldn't be as valued. Of course, it all depends on the type of volunteer work done, and the type of job being appied for.
Volunteering to build a house for habitat for humanity doesn't help you a job as paramedic as well as being on the volunteer ambulance service for a small town.