My university is switching its Virtual Learning Environment (VLE). Specifically, we are moving from WebCT to Moodle, but I don't think this matters. This means I need to spend some time learning how to use the new software, but it also presents me the opportunity to think about how I use a VLE to supplement my traditional teaching. Are there any references of how to best leverage the use of VLEs?
WebCT is probably about as user unfriendly as it gets so you'll probably find moodle pretty easy to pick up after that!
I recommend you to try a demo site of Moodle. It would be specially helpful to try one that has content. Here you can find one. You can choose which role to use, so you will be able to see what students see and to see some settings for each activity.
Moodle's documentation is the bible for using Moodle. You just have to make sure to review the documentation of the current version of your site. For instance, the capabilities of versions 1.9 or lower are much more limited than those of versions 2.0 or higher. However, if you are beginner I suggest you to visit first the demo site. Moodle's documentation could be more difficult to grasp if you do not know how a site works.
I am not sure if you are going to use Moodle as a support for classes ("blended learning") or if you are going to teach an e-learning class. However, regardless of the kind of use, here you can find interesting ideas and concepts about distance education using Moodle. These ideas will be useful even if you are teaching a blended learning class. This document explains some principles for distance education (e.g., the course interface should be simple and intuitive).