I've used both approaches. My suggestion is to use contract first schema, but code first WSDL.
Writing a WSDL file has a lot of weird nuances like bindings, ports and such. I'd rather have this done by tools rather than by hand. There are tools to help do this, but none of them are simpler than
@WebService
public ...
At the very least you can verify your deployment.
For the schema, I suggested contract first because the XML Schema language is far richer than what you can describe in Java. An example I usually give is showing that XML Schema can restrict the size of a string and apply a regular expression pattern. Doing that in Java and annotations looks a bit messier.
Another advantage of doing the schema as contract first is the presence of tools to convert your schema file into HTML documentation.
The XJC tool can generate the requisite class files. However, I would only recommend doing that at start.
In the end you should take the generated WSDL file and work with that instead. That way you can use wsimport and verify that the whole thing from WSDL to Schema is valid.
You can deploy with the WSDL file by using the wsdlLocation attribute in your @WebService implementation and the application server will fix the binding data for you when users request the WSDL from the server, but you still retain your annotations. Otherwise your annotations will not appear on the requested WSDL files.