Rinse dust or dirt from exterior caulk using a hose. Wait three to four hours for the surface to dry. Dust interior caulk with a coarse plastic brush. Wipe the caulk with tack cloths to promote adhesion.
Protect areas you do not want painted that are beneath or adjacent to the caulk. Cover these areas with painter's tape and drop cloths.
Coat silicone caulk with an oil-based primer, using a 2-inch natural-bristled paintbrush. Wait two hours for the primer to dry. Wash the brush with mineral spirits.
Coat acrylic and primed silicone caulk with latex paint, using a 2- to 3-inch nylon paintbrush. Wait two hours for the paint to dry. Wash the brush with water.