start off small just to get your face out there. Once you start volunteering, you will like it.
Go to Sams Club/costco (sp?) and buy a bunch of bulk breakfast food (sausage and biscuits, orange juice) and serve the food at a homeless shelter a fewmornings. Just get to know the people first. From there, you will learn of their needs and other places they frequent to get services.
The goal is to network with other non profits in your area ,no need to rebuild the wheel at first. You'll hit a creative spark somewhere.
other ideas for your program: Resume, interview skills, computer skills, learning how to read, helping their kids to learn basic math and reading skills, howto start a business, etc.