Or paint, then silicon..
around tub enclosures and baseboards?
Paint does not stick to silicone. Where painted surfaces meat the fixtures I use paintible caulking with silicone and I caulk before painting.
Agreed, paint doesn't adhere to 100% silicone caulk. There are, however, many paintable caulks -- it'll say "paintable" right on the tube -- that contain silicone as well as good non-silicone products like Phenoseal.