Hi Wil,
-TR_times sets up the time grid size when you output the impulse response function with option -iresp and the associated standard deviations with option -sresp, and would not have effect on anything else. And it does not have to be the same as your TR (and can be finer).
Your setup with -stim_times seems fine to me. It is not expected the result from 3dDeconvolve would be exactly the same as the one from SPM because there are quite a few things different in terms of pre-processing and modeling strategy. But how different are they and in what sense?
Gang