In general S/PDIF is likely to have less jitter but an asynchronous DAC will greatly reduce the impact of jitter. S/PDIF connections are often less noisy than USB connections, but for the case of a PC in particular I would not expect that to be true since ground noise injected into the signal is probably similar for either source from a sound card.
My guess is you are unlikely to hear jitter with any decent DAC.
My guess is you are unlikely to hear jitter with any decent DAC.