Peter,
When I used non reflective slits I had Al's Reticule great freeware to produce a "virtual slit" gap and then just dropped the target star onto the double cross wire.
I assume you have a reflective slit? Use the reference lamp to illuminate the slit ( same as you would do to focus the guide camera on the slit) and note the X/Y of the slit centre and the Y value to the slit length.
You can then use these coordinates with the "lock-on" function of PHD (or with the spectro guide function of Astroart) to accurately position the star image on the slit gap.
Once the star is on or very close to the slit the slight change in the star shape guides you to the slit centreline - a nudge of +/- one pixel usually does the job.
As terry says just check the max ADU of the spectrum to confirm you're getting best signal.
Hope this helps.
(Over on the Astronomical spectroscopy forum, there's a write up in the files area detailing the "Al's reticule" method - Setting up Al's.pdf)
https://groups.yahoo.com/neo/groups/...troscopy/files