ISO 100 will always produce better images than ISO 400 assuming that both are properly exposed. That is, the noise will always be lowest at ISO 100, so the image will also hold more detail. However, ISO 400 is so good these days that the difference may be almost impossible to see even in a 12"x18" print. My standard ISO is 200, but I'll go up to 800, 1600, or 3200 if I need it for low light without flash.
There are only two possibilities for why your ISO 400 may have been better than ISO 100:
1. Something was moving in the scene (wind in the trees? subject motion?), so scene motion was frozen better at a higher shutter speed using ISO 400.
2. If the exposure change between ISO 400 and ISO 100 was accomplished by opening up the aperture by two stops, then ISO 400 could well have been shot at the best aperture for each lens (typically about 2 stops down from wide open), while ISO 100 was shot wide open and thus not at the optimum aperture.