Before you start cleaning the limescale from your pool walls, you'll need to drain your pool. You don't have to drain the water completely--just enough so the calcium deposits are fully exposed. Not only does draining make it easier to see and clean the limescale, it minimizes the amount of cleaning chemicals that get into the water, possibly causing imbalance. If possible, set the water aside in buckets or a kiddie pool so you can reincorporate it when you finish cleaning.
Several pool cleaning solutions are designed to remove scale and calcium deposits from your pool walls, including LimeAway, Jack's Magic Blue Stuff and Blue Wave. These come in gel form, allowing you to apply them directly to the limescale without worrying about the solution dripping into the pool. Typically, you need to leave the gel on the scale for about 10 to 15 minutes before scrubbing with a non-metallic scrub brush. For an all-natural alternative, spray white distilled vinegar or apple cider vinegar onto the scale and let it sit for five minutes before scrubbing.
No matter which solution you use to remove the scale, rinse away any residue before you refill the pool. A bucket of clean water and a rag is all you need. Don't just spray the walls and let the residue run into the pool. Once you rinse the walls, you can refill the pool. If you reserved the water from draining, dump it back in. Otherwise, refill from a garden hose.
Allow your pool to sit with the pump running for about four hours so the chemicals can equalize. Test the pool with a pool water test kit. If you refilled the pool using the drained pool water, the effects on the pool's balance should be minimal. If you had to refill from a hose, you will need to adjust the pool's chemistry so pH and chlorine are at optimal safety levels. Chlorine should be 1 to 3 parts per million, and pH should be 7.2 to 7.6.