Removing it after it warms up would be bad. Think second degree burn bad.
Normally you would drain enough coolant to prevent overflow expansion (a pint or so should do it) and then warm the engine up with the cap off. That's typically the method using the archaic POS (imo) kit Napa sells.
Fwiw some leaks only show up when the engine is cold or cooling but they're not all that common...