This one help a bunch when getting started, it shows the items types and how to create a basic and advanced map:
http://kolmafia.sourceforge.net/advanced.html
The best help that I got were from user created scripts found here in the forums. I think I have every script in these forums downloaded in a file somewhere. If I have a question on how to do something first I browse through the ones that I have, if that does not help then I ask questions.
What is your programing experience? Knowledge of Java is not necessary but some upper level programming is probably necessary. If you don't have any I would recommend you pick up a cheap teach yourself programming book somewhere. It really does not matter what language, I trained in C++ and made the transition to ash pretty easily.
A few more things that helped me:
Type this in the CLI and copy/paste the result in a file for reference:
help
ashref
Download the source code for mafia and in the data folder you will find all of the item maps that Mafia uses internally, this helps a bunch on how to spell items correctly, zap groups, recipes, etc.