Simplex - Transmit and receive on the same frequency. Does not use a repeater.
Common simplex radio systems include SPEN, JEMS, FRS radios, CBs, etc.
Simulcast - Transmit from multiple locations/multiple frequencies at the same time (simultaneous broadcast).
Its used so that units in different areas or on different radio channels can all hear the same transmission at the same time. For example, the NJSP trunked radio system is simulcast so that units in the range of different radio towers can all hear the same transmission. Or, if you are switching from one radio system to another, you will often simulcast on both for a while to easy the transition.