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I have done this many times. The key is to have a business card, preferrably with a clear example of your art on it.
Introduce yourself, hand them your card and tell them that you are a painter and are always looking for attractive people to model, you saw them and you would love to use them in a painting or two. Tell them that you will give them a print of whatever you paint with them in it, and last tell them what you will pay them per hour. Tell them that they should call you if they are interested, reference that they can see more examples of your work on your website and then walk away. It works well.
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