That tab is what you use to keep connectors tidy to the frame. That one may well be the rear brake light switch connector. The connector has a moulded part which just slips over the tab. There should be about 3-4 across the frame. Just bend it a bit to get paint on it and gently bend back once painted.
Powdercoats cheaper and tougher, but as you said can be annoying if they do too thick in some areas. Paint is good but more expensive to get done.
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