You can start here:
- Introducing JAX-WS 2.0 With the Java SE 6 Platform, Part 1
- Introducing JAX-WS 2.0 With the Java SE 6 Platform, Part 2
NetBeans has really good support for JAX-WS and plenty of tutorials are available, e.g.:
- Getting Started with JAX-WS Web Services
Glen Mazza's has written plenty of interesting articles on JAX-WS RI / Metro:
- Web Services on Glen Mazza's Weblog
The JAX-WS web site references good resources:
Finally, the JAX-WS RI includes many sample for lots of use cases that you can checkout from:
Or just download and unpack the JAX-WS RI.