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A lot of college pole vault coaches are volunteers. I even know of a few that are teachers. Would there be any kind of rule against a coach volunteering at a High School and College? I know there are rules about college coaches coaching clubs and how there could not be another club x miles from the high school kid and how they have to pay and stuff like that, but not clear if that is just for paid NCAA coaches.

The rules vary by NCAA Division. When I was coaching DII a few years ago, the rules specifically allowed a volunteer coach to also coach HS, but I think DI you couldn't do this.

To answer your question, generally all NCAA rules apply to volunteer coaches. It's important to talk to your compliance officer and make sure you know what the rules are in your specific situation.