Canons in particular have a high level of variability in shutter lag, so even firing on the second curtain, you are probably going to get some black frames. It is definitely important to prefocus cameras before firing as this greatly reduces the variability in shutter lag, but it still happens. Most reliable is to introduce the delay as suggested, for which the formula is:
1) Set shutter speed to be somewhat long (1/10 generally as mentioned by many)
2) Introduce a delay for the strobe firing that is 1/2 of the shutter speed, for best chance of all shutters being open when the strobes fire.
This is the approach that I have used to great success, you can get the shutter speed lower still even, but why bother when this works 100%.
In our case we use a PocketWizard Plus X (cheapst model) to transmit the signal, and MultiMax to receive the signal and introduce the 1/20 second delay before passing the signal on to the strobe. I believe a Camera Axe will allow you to do the same thing for cheaper, but requires a bit more work to set up.