Yes, you *CAN* use the ST-E2 to trigger a strobe in the manner that you are seeking.
1. Put the ST-E2 on the camera in the normal way.
2. Have your 580EX (or other Canon wireless flash) *OFF* camera, and set as a SLAVE.
3. Press the <MODE> button on the 580EX for 2 seconds. <M> will blink. THIS DISABLES THE PRE-FLASH and stops the other flashes being triggered prematurely.
4. Now set the manual flash OUTPUT on the 580EX in the normal way. You can use the 580EX as your "main", "fill" or background light, OR turn the output right down and simply use it to trigger the other studio strobes via their optical slaves.
It works really well. I use it when I'm shooting with a light tent for macro photography. I have the 580EX as on of the main lights and I use that to trigger a couple of old Panasonic flahes I've had for 30 years.
**See page 43 of the 580EX instruction manual.