Carbaryl was the recommended caterpillar spray a few years ago, but it's nasty stuff. I have no idea of its safety on cacti, though. I suspect it's no longer available due to toxicity concerns. Malathion was another nasty one, but honestly organo-phosphate poisons give me the heebie-jeebies. Dimethoate (Rogor) is one that I have used, but it's still pretty nasty. Confidor seems to be a popular systemic insecticide, but I have no idea about its effectiveness against caterpillars specifically.
I personally favour squishing 'em manually.
On a related note, I reckon Opuntias seem to be snacked on by more pests than pretty much any other cacti that I've grown. Snails and slugs seem to love them, and *something* - I'm yet to work out what - has been going the munch on my feral O. monacantha. That said, if it distracts them from my valuable plants, I'm okay with that...