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I'm replacing the caulk on my bathtub/shower, since it's in sorry shape.

See the images below. My house is about 50 years old and I believe these shower walls are original. They appear to be some kind of resin. For the interface between the (porcelain-covered cast iron) bathtub and the shower wall, I'm planning on using 100% silicone caulk. However, I understand that 100% silicone caulk isn't the right thing to use on paint or porous walls. What kind of caulk should I use at the interface between my shower walls and the sheetrock wall?

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You probably want an acrylic/latex caulk for where the tile meets the painted wall. You can also use a blend of acrylic/latex and silicone in that application, which has better waterproofing characteristics.

You can use "pure" silicone but there are problems with that. Silicone calk won't take paint very well if you decide to paint the bathroom wall and want to cover it, and that might not be a problem, but also when it comes time to replace the caulking in about 15-20 years, the silicone will likely pull off the existing paint and drywall paper before it comes completely off.

The acrylic/latex caulking will take paint (if that's what you want to do) and will come off without doing a lot of damage to the painted drywall surface.

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