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My advice is start learning both, look for a simple tutorial. When you've played with both for a bit go for the language that you feel more comfortable with, if you are working with a language you actually like you can be more productive.
HTML first, still the standard.
CSS second, growing by leaps and bounds.
Linux third, gotta have the basics of shell accounts and apache.
XML fourth, stands to grow fast.
js, pick up the scraps and learn how to find code...you should rarely have to write your own from scratch.
SQL, all larger websites will use SQL - you need to know how to use it.
PHP in a pinch, but very few larger companies are running it. It is basically relegated to some sectors of the net.
perl, I've yet to see a good website that didn't have some perl on it someplace (even if the admin didn't know it). The basics of perl can be learned in a week.
What is vbs? ;-) I can't imagine ever needing to know vbs.
if you have that long...a while back I hired a subcontractor to produce a PERL chatroom for a project based on the total eclipse...11pm the night before with 9 hours till it happened he hadn't set the chat room up and couldn't be contacted on the phone
by 8am the following morning I'd managed to find a chat room CGI I liked, learned enough PERL to alter it to fit with the site and the parameters required, uploaded and tested it
you can be tampering around with existing PERL scripts in a matter of hours entirely using web based tutorials