Josh,
To monitor the physical onset of the stimuli, you'd need a photosensor that is rigged up to a timer that is synchronized with Inquisit. If you are an electrical engineer, you could build this yourself as it's not super complicated. If not, then you might look into purchasing Blackbox Toolkit, which has preconfigured photosensors among other things. However, if you are conducting research over the web on participants' home and office computers, that's not going to be very helpful.
With tachistoscopic presentations, there are two things to look out for - a given stimulus is presented too early or too late. The way Inquisit is designed, it would be very rare for stimuli to show up too early, and if this happened, it would likely be due to a messed up video driver that doesn't properly signal vertical retrace status. (Even then, Inquisit would likely detect the problem and simply throw an error.)
Stimuli can show up late if the time required to load them into video memory exceeds the duration of a retrace interval. With modern video cards and CPUs, this should also be quite rare unless you are presenting very very long sequences of high resolution images on an older machine.
You can detect either case via the stimulusonset parameter. Each stimulusonset should be on the border of a retrace interval, plus or minus 2 milliseconds or so. For example, if you are presenting a stimulus at the 3rd retrace on a 60hz monitor, the stimulus onset should be around 50ms. That marks the time point that the stimulus is completely loaded into display memory, so it will appear on the monitor on the next refresh cycle. The 2 ms fudge factor is because the vertical blank interval itself (the period after a refresh is complete and before the next one begins) takes some time. Also, since memory is drawn top to bottom, the fudge factor for stimuli on the bottom of the screen is actually a little greater.
LCD monitors do introduce pixel latencies into the mix. On most LCDs, it takes a given pixel anywhere from 4 to 20 ms to fully light up once the graphics card has instructed it to do so. The latency will also vary depending on the color, with high contrast (e.g., black to white) transitions being the fastest. LCDs are getting faster, though, and companies are coming up with new technologies to speed up the pixels. This is primarily being driven by the gaming and movies.
P.S. Just for the record, there is no performance penalty for using different pictures formats (jpg, bmp, gif, etc) in Inquisit. Inquisit loads and translates all pictures at the beginning of the experiment into a native Windows format, so once they've been loaded, they are all the same format. I thought it was worth pointing this out, because I know that's not how some other experimentation packages work.
-Sean