1. Just add the Distilled water slowly so that you don't bring your salinity down to fast and shock your critters. Distilled water is run through RO/DI before it is distilled, so it is fine. The high salinity could have contributed to the death of the fish. Just one more source of stress. It makes the fish's kidneys work harder trying to maintain their fluids levels.
2. I assume you are using a solid calcium supplement like Turbo calcium. You can't add it as a solid. That is a waste of product and time. It just causes your alkalinity to fall because it precipitates as calcium carbonate. It needs to be dissolved in the distilled water first and then slowly dripped in. I agree that calcium is not a major concern right now. I would be more concerned with your alkalinity. You can do the same thing with solid buffer to raise your alkalinity. However, in a tank your size, supplements shouldn't be a big issue if you are doing weekly water changes.
3. Get a reliable test kit for ammonia and nitrate that gives you an actual numerical value. Those stick in the tank things are only good to let you know you have a problem when a crisis occurs, not as a good way to determine actual values or how bad the problem actually is.
4. The little starfish are probably asterinas star. Do they have 6 legs and look like a Jewish Star of David? If so, that's an asterina. Some people freak out over them and say they kill corals. I have hundreds in my tanks and have never had a problem with them. The only good way to get rid of them is a certain kind of shrimp that you are not ready for right now anyway.
Hope that helps.
Gary
125 SPS, 75 gal. LPS/softie reef, 9 gal. Nano