Via the test/meter buttons, only the selected channel will fire. Via the hotshoe or PC connection, all will fire regardless.
The exception is if you select a group (GRP). When in a group, only channels assigned to the group will fire via the buttons or hotshoe/PC. If you were in ALL and scrolled once to the left, you would enter the groups settings (GRP8, specifically) rather than revolving to CH16.
Incidentally, which light is "that light". Is it the speedlite? If so, make sure you have the light defined as Speedlite via the SPEC LIGHTS screen (if you have done this "speedlite" will appear in blue in the lower right when selected). To do this follow the steps on the bottom of pg30 and top of pg 31 in the manual:
http://www.paulcbuff.com/manuals/cc.pdf If the speedlite is not defined, it may trigger at times when it is not intended.