Going door to door searching for jobs. What's a good way earn rapport when you first walk in the door? (Design / Marketing type work)

So I've recently been having trouble landing employment relative to my skills (marketing / design) and I've resorted to an old-school method of finding nearby businesses and dropping my resume into someone's hands at different places. I've come very close to one lead where an employee mentioned quickly off the cuff that they are hiring in the near future, and I want to maybe show initiative by trying to get face-to-face with someone in regards to employment.

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What are some good tips to follow so I don't come off as overly pushy or annoying and maybe earn enough rapport with someone in such a way that in the event they may not immediately offer me something, but may give me a call if a seat opens up?

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To be more specific with this one lead, I'm right now headed back to college in a few weeks to continue studies for my Master's degree and I want to find a semi-full or full-time position that's willing to work around my school schedule while I go for my degree. I found a listing for this company hunting for a part-timer on a job board and I think I'd be a good fit with this place because it's a small startup (only 4 people work there), they want a part-timer and not a full-timer, I have relevant experience relating to their business, and I think getting design agency experience would be ideal for my resume rather than going from place to place that is looking for a designer either temporarily or just for this one company.

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