Employment strategy - be patient, or apply early? Should a person start applying for careers prior to completing education?

I've considered internships, but have had little luck finding anything. I chose instead to pursue volunteer work that I could use to create a portfolio and build my resume. I took on a volunteer position with my city's fire department, where I was quickly promoted to Treasury Secretary after obtaining the city a substantial $120k grant for the acquisition of new personal protective equipment, I digitized and organized a highly disorganized and outdated system of record keeping, and I am currently working on writing another grant request for the department to obtain for them a $300k grant to replace our Tanker, as well as a grant for the city to rebuild a 100 year old playground. Keep in mind, the "town" I live in, has a population of about 300 people, and the equipment that had been in use by the Fire Department was over 30 years old. I felt that roles like this, and potentially a city council role in the future would lay the groundwork for detailed accomplishments that would be hard to come by with internships meant for 18 year-olds with no life experience, but that plan involved putting off the application process for a few more years, which gave me time to complete my masters.

Volunteerism is a good resume' enhancement... but doesn't pay much :-) ... look at non-profits. From time to time they have openings. They do n't pay much but they give out REALLY IMPRESSIVE SOUNDING job titles in lieu of pay... long hours, shitty jobs... but fiil space on the resume'

Thanks CAPT Kevin B., those were some of my concerns. I had several people using the "what's the harm, worst case scenario they don't hire you" line out there, but I was concerned on how it would impact my reputation. I'm not so concerned about that, because I am looking to move when I do finish my schooling (or before if I got hired) so I am not likely to apply to the same position twice, but I still would prefer not to have a reputation that gets my resume tossed before anyone sees it. I'm also a bit unsure about what height to shoot for. When I finish my degree, I will be 31 years-old with a BA in International Politics and a Master's in Community and Economic Development, with 9 years as a Civil Affairs Specialist in the USAR. Other than that, I have several short-term roles like a volunteer state coordinator for a presidential superpac and a very successful stint as a Treasury Secretary for the local fire department, but other than that, I have very little in the field of ACTUAL experience in the job. I would like to think that with the education (and not being 21) I would be able to shoot for a higher level position off the bat, in a smaller town, but is that being unrealistic?