It'll probably peel and crack off - a lot of house paints are now water based (at least here). From what I've read, your boots may have a glaze on them to protect the leather which needs to be removed with acetone (needs cleaned off after to prevent eating away at the leather beneath the glaze) before painting that area.
What does the finish on your boots look like? And how/what do you want to paint them like? There are spray cans that others recommend like these here.
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