According to your web service knowledge you might want to take a complete tour of the JBossWS documentation or skip some topics. This most probably also depends on your role and responsabilities in the enterprise project you need web services for. Below you'll find some suggestions on the pages to read given the user experience; you should start from the paragraph that best suites you.
Non-technical users and web service newbies
People with no previous knowledge of the web service technology platform should take a look at the WS Culture category's pages. In particular the Web Services page has a very high level introduction explaining what this is all about, while From concepts to technology provides the minimal general technology information you can't miss.
This should give non-technical users an idea of what web services are and why you would use them or not. Developers willing to use JBossWS should be able to proceed to the next paragraph.
Users with web service concepts' knowledge
Developers with basic web service technology knowledge and no JBossWS experience should start with the Start from scratch category's pages. In particular the suggested minimal path is
With a productive environment well set up, they'll be able to start developing; thus they should proceed to the next paragraph.
Finally, the FAQ pages is available for quick solutions to common questions.
QA testers and system integrators
The production category's pages should be consumed by advanced users and system integrators willing to perform fine tuning of their WS system, take care of security, accountability, statistics and availability issues, etc.
Finally, QA testers and developers working with them would probably be interested in reading articles from the category. Those pages provide hints for making the QA phase of a web service application easier as well as some directions on how to setup logging.
Project contributors can find the technical information, design topics, etc. in the JBossWS - Contribution category's pages. Users willing to get started with JBossWS contribution should read the first.