I took the exam earlier this year and it was definitely worth it. After all, it's pretty affordable if you don't take the courses from Zend. It has really improved how people recognize me as a serious developer and not as some "guy who hacks dirty php scripts".
I used the "ZCE PHP 5 Study Guide" published by php-architect to get an overview of the topics and then I went through the PHP online manual mostly. I also wrote a lot of example code to try out the stuff that I had not used before.
Preparation took me about 3 months since I had to do it in my free time and you should absolutely take enough time to prepare and study. Some questions are really mean!
In my opinion a large portion of the required knowledge can not be taught by reading books. There are many questions that you can only be answered with real world experience.
The questions are pretty much about everything that a PHP developer may encounter in his work. From basic syntax and databases over object oriented design to website security, best practices and code maintainability.