Mackay,
Did you take a test photo with all flash units visible in front of a mirror as recommended in my previous post?
You can NOT trigger an optical slave with the built-in flash.
The built-in flash fires two strobes: a pre-flash strobe and a main flash.
The pre-flash strobe, for light metering, happens before the mirror raises. The mirror has to be in the "down" position because the light sensors are in the prism. The light entering the lens needs the mirror bending the light to hit the light sensors.
The main strobe is to illuminate the scene during metering.
The problem is that the optical slave is triggered by the pre-flash strobe, firing the external flash
before the exposure. Thus the external flash does not fire (not enough time to charge up) during the exposure.
The pre-flash strobe and the main strobe, in normal case, are only about 1/50 second apart. Most people can not tell that there are two strobes.
To verify this, set your camera to 2 second delay mode. After hitting the shutter release, you will see in sequence: the pre-flash strobe (and the external flash firing), the mirror raising, 2 second delay, the shutter opening (and the main strobe from the built-in flash).
The only case in which the built-in flash fires ONE strobe at full power is when you have a manual lens (non A) attached to the camera body.
See
this thread for similar problem (a bit more complicated, but the cause is the same). My post is on page 2.