My guess is calcium from your hard water. Try soaking and scrubbing with starsan, maybe a slightly more concentrated solution. Lactic acid or CLR might work as well. I have hard water as well and rince my fermenters, kegs and bottles with a bit of starsan after cleaning to help reduce this.
Using PBW of cheaper cleaners, as you're already doing, is a good thing to do with hard water. It has additional additives that are meant to prevent the buildup, but I guess some water can be just too hard.