Regular old Hydrocortisone creme works well for me.
No, it's not from chafing, and no, it's not from the elastic band. For me, it only happens occasionally, in high heat and sun, under my shorts/lycra, only on top of my thighs. Sometimes it fades away after the ride, sometimes lasts a day.
I suspect it would not happen if i were wearing my merino wool knickers, which breathe well and are a more natural fiber...but they would be too hot to wear on a really hot day, so I won't be testing it!
INterestingly, one time I was sitting in the hot sun in my bike shorts, pre-ride, and felt that itchy irritated feeling of them starting up on my thighs. I went to the ladies room, saw the blotches starting up there, and put some sunblock on my thighs under the shorts, simply because it was the only lotion I had with me. It immediately faded away and did not return even during my ride that day in the heat. Odd.




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