We report on the single-shot readout of three two-electron spin states-a singlet and two triplet substates-whose z components of spin angular momentum are 0 and +1, in a gate-defined GaAs single quantum dot. The three spin states are distinguished by detecting spin-dependent tunnel rates that arise from two mechanisms: spin filtering by spin-resolved edge states and spin-orbital correlation with orbital-dependent tunneling. The three states form one ground state and two excited states, and we observe the spin relaxation dynamics among the three spin states.