1. What is jittering?
It's the practice of varying the timing of your TR relative to your stimulus presentation. It's also often connected to, or even identified as, the practice of varying your inter-trial interval.
The idea in both of these practices is the same. If your TR is 2 seconds, and your stimulus is always presented exactly at the beginning of a TR and always 10 seconds long, then you'll sample the same point in your subject's BOLD response many times - but you might miss points in between those sampling points. Those in-between points might be the peak of your HRF, or an inflection point, or simply another point that will help you characterize the shape of your HRF.
If you made your TR 2.5 seconds, you'd automatically get to sample several other points in your response, at the expense of sampling each of