Photoshop = design it
Dreamweaver = build it
Thats your best shot...
About a portfolio, i will say smth i did and i know a few people did it: you can start creating designs for fictional companies, several segments, build a portfolio showing it, and that is it... dont need real clients to start a great portfolio... your clients will want to see your skills, is what matters.
later you will surely replace fictional clientes with the real ones... i started in 1998 doing this, and was great... (the real client dont need to know that your portfolio is fictional) ))