You know when to use CPCTC by the "prove" or "show". If the question asks you to prove that two sides or two angles in different triangle are congruent, use CPCTC. Be careful of more complicated proofs where you need to show two sides or angles are congruent and then make the "prove" or "show" statement (like proving the isosceles triangle conjecture); you will need CPCTC for this as well.