I think if you're really considering being a web developer, you should at least be familiar with the basics of the "big five" : Perl, JSP, ColdFusion, ASP, and of course PHP. I suggest writing at least a simple shopping cart in each language. Shopping carts are good applications to practice with because it brings forth solutions that are used in general applications. That is session handling, database access including design and SQL, security, XML; the list goes on. I suggest being familiar with each so you know the ups and downs of each. It's not enough to just follow someone else's opinion... it's better to see it yourself; what's so bad or good about a particular language/method. When the time comes around to handle a problem upon request, you can then make an intelligent decision on what to go with (ColdFusion, PHP, etc.). Of course this comes after seeing what the budget is, who's working on it, who will be maintaining it after you leave, what tools (servers, IDEs) you will be giving, how easy it is to debug/extend/upgrade, and how much time you have.
Bored with ASP? Every language itself is boring, what makes it interesting is how you use it, not the language itself. Every language can pretty much do the same thing, just the syntax is different. If you feel "bored" try to extend whatever language you're using to other technologies. If you haven't looked into these, here are some topics to keep you occupied:
Coding Methologies (component reuse/extending)
Internationalization and Localization
Handling Sessions throughout Clusters
Regular Expressions
Optimization
Scaling
Security (Server, Database, Application)
Web Services
XML, SOAP, XSL/XSLT
Database Theory (Diagrams, Normalization - 1NF, 2NF, 3NF, etc.)
CORBA, COM/DCOM, ActiveX, Services
Application Framework (n-tier, .NET)
WAP (Wireless Application Protocol) - Wireless programming
Of course, you can't forget good ol' JavaScript, CSS, HTML, DHTML, and XHTML. Also, the use of databases, Oracle, SQL Server, DB2, MySQL, PostgreSQL, Sybase, through whatever language you're using.
These are some topics that relate to whatever language you use. I hope you find them useful.
But anyways(man, I
REALLY got off topic there...

), you wanted to learn PHP, and wanted some good resources. I recommend two good books which got good reviews at Amazon.com:
PHP and MySQL Web Development by Luke Welling, Laura Thomson
A Programmer's Introduction to PHP 4.0 by W. J. Gilmore
Some good sites are (besides php.net):
http://www.phpbeginner.com/
http://php.weblogs.com/
http://www.phpbuilder.com/
http://php.resourceindex.com/
http://www.phpworld.com/
http://www.devshed.com/Server_Side/PHP
Another tip is no matter what technology you're "mastering," always keep up to date with other technology. You don't have to use it, but just keep up with what's new by visiting Builder.com, Slashdot(which sometimes I despise, but I'll let that go for now), C|Net, etc... you can think of others.