PCStitch 10 (and PCStitch 11) include a PDF user's manual. There should be a shortcut for it in the same shortcut folder that includes the main program. There is also a tutorial available under "Help" within the program.
One other piece of advice (and this is a personal comment) -- PLAY WITH IT! Just click and look and see what happens. You can't hurt the program and you learn by making mistakes and reading. Just have fun.