Matron: Matron's main duty is to take Tired girls off duty, and then put them back on duty when they're rested again. Takes a personal job off your hands. (Slaves cannot be matrons.)
Torturer: Torturers, well, they torture the girls you have in prison, if you're trying to break a girl. Again, takes a personal job off your hands, plus they don't accidentally kill girls. (Slaves cannot be torturers.)
Beast Carer: Takes care of any beasts you have! Beast Capture or Catacombs will bring beasts in, Beast Carer will make sure they don't die and help them reproduce.
Customer Service: Customer Service makes the gambling hall, when active, get you more money*.
Singer: Singer makes the bar, when active, get you more money.*
*Honestly assumptions, haven't strictly tested them, but seems sound in my experience.