Not bloody likely.
Even primitive man was not an idiot.
Spend weeks engraving a perfect sphere to kill the Sabre-tooth Tiger, when there are a gazillion free rocks scattered everywhere?
Maybe if the hunting had been poor and the people really hungry, they’d use a ‘magic ball’ to increase their chances - made and saved-up for the lean times ;-)
If you want a rock that will stay in it’s bindings and fly true you will. It’s not like they had much to fill their free time with anyway, so why not spend some on improving the important objects that provide food and protection?