most kings need a few weeks and several meals before they are ready to breed. You will probobly notice that your male is getting randy before the female has actually ovulated. If you do not know how to palpate the female to tell when she is ready then the easiest way to tell is just to put her in with the male for a few hours every few days. If she scutes away with her tail shaking, she is not ready. If she is ready she will crawl slowly and let the male crawl on top of her. Just keep a careful eye on them at all times.
The shedding happens to be a convenient mark for around when a female will ovulate, however the two cycles are not directly related. I have seen kings breed long before, and long after the first shed of the season.