First, you need to fully understand what each application is used for and when. What is your profession? Are you a photographer? Do you want a job in a print shop? Are you a hobbyist? Are you an illustrator? You say you are an expert in Photoshop. What color mode do you work in? Have you worked with paths? If you are just starting to teach yourself Illustrator, start with creating a new document and database for project management. Get to know proper file setup including fonts, images, and supporting pieces of artwork. Get Adobe's Print Publisher's Guide. Read it thoroughly to learn basic terminology, advanced terminology, color, color spaces, working with shapes, etc., etc.
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