Page 7 here shows you the basics. Basically add or try to use a PID somewhere (graph, histogram, gauge, whatever). At the bottom of the list of PID's there is a 'configure user defined' option, double click that. Then you can make whatever PID's you want in the window that comes up.
Make sure you add all PID's that you use in the custom PID's to the table display. Otherwise it won't be logging what it needs to make use of your new PID's
Also, try to use PID's instead of SENSORS, despite what the fine text says in some of those windows. Sensors have never worked well at all for me in 2.24
If you're starting from (close to) scratch knowledge wise on HP Tuners, you might consider going ahead and going straight to the latest version (V3). It's a big change from 2.24, but if you don't know 2.24 well and are going to have to learn anyways, you might as well learn on the latest one
In my opinion anyways.
http://wot-tech.com/pdf/Setting%20up...F%20tuning.pdf