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Rubbing alcohol has been proven dangerous to continuously breathe in. Using pure vodka, which is a pure alcohol is much safer. A bit more expensive, but the risk with rubbing alcohol is too high.
Any acid based or bleach based cleaner will corrode and loosen your grout. This includes vinegar. If your grout was not sealed properly, you will need to clean it as best as possible with non-corrosive products, then buy "grout colorant" to cover the old stains, and finally seal it properly with a grout sealer. As far as the caulking goes. If you are getting discoloration and mold quickly, you probably have the wrong type of acrylic, bath, caulk installed. With regular cleaning, you shouldn't get the black mold.
I stood over the edge of my bathtub while pouring peroxide over a cut on my foot. When I finished, I noticed that the peroxide had cleaned the grout and side of my tub where a rust stain had been. I had tried EVERYTHING to get that rust stain out and accidentally pouring peroxide on it cleaned it within seconds!
I don't know about cleaning the grout. As for the caulk, if it looks really bad I would simply replace it. If you haven't done this before, they can explain it to you at Home Depot or check out google. It may be easier and faster than lots of scrubbing.
I too, would use bleach, or rubbing alcohol, which is 50 cents/pint. Bleach kills mold and mildew, just don't get it on carpet, or use with ammonia. (toxic fumes)