I don't have the diagrams for the RAV4 specifically, but most Toyota HVAC systems follow the same basic design and many share components.
The his-&-hers heater has a split plenum and separate air-mix dampers to keep left and right air blends apart. You are basically regulating how much system air flows thru the heater core at the lower section of the HVAC box before heading to the mode damper (floor/vents/defrost).
If you have heat on all the time just on one side, something is amiss with either the Servo controller, the motion arms off the servo, the damper shaft, or the flaps attached to the shaft that route air into the heater core. If it's like other Toyota's, you can probably remove the glove box door and maybe the lower dash panel and get to the servo body.
Other issues that it could be:
Most Toyota's have gone to CAN buss, and each servo in the system (there are up to 4) has a microchip that's sync'ed to the HVAC Amplifier (the brain). It could have lost communication and need to be re-initialized, the chip in the servo could be bad, the wiring could be bad, or the Amp or front panel control could be bad.