主演(しゅえん):starring; playing the leading part
主:chief; lord; main thing; master; principal
on-reading シュ、シュウ、ス. kun-reading あるじ、おも、ぬし.
主(あるじ):1. head (of a household); proprietor (of a store); proprietress; landlord; landlady; master (of a servant) (abbreviation)
主(おも):1. chief; main; principal; important 2. main secondary or supporting role (in kyogen) (abbreviation)
主(ぬし):1. head (of a household); leader; master 2. owner; proprietor; proprietress 3. subject (of a rumor, etc); doer (of a deed) 4. guardian spirit 5. husband (pronoun) 6. you (familiar language)
演:already covered here.