Well Simon, many of the tasks both systems do are going to be similar your experience will help. But at the same time expect it to be different. In the main it provides you with the freedom to work as you chose. Like most freedoms the powerful benefit and the weak lose out, and in this case knowledge really is power.
Keep an open mind that's just the secret to learning anything really. NX is a hybrid modeler not just a sketch based system, or a surfacing package. You can stick to what you're used to for your own purposes but when you start to work with other people's data you may be shocked to find it somewhat anarchic compared to what you may be used to. I find that people who judge any system by the standards of their favorite are apt to be over critical and do themselves a disservice by rankling against the differences. In many ways NX is about as powerful as a CAD system can be, sure there are Pro's and Con's with any comparison you care to make but I'd like you to try starting by getting and overall sense of what is possible. At least that way you'll be embarking on a journey of sorts that has some sort of desirable destination, whereas many just experience a new CAD system as a series of rather pointless trials whereby they endure change without appreciating the purpose of doing so beyond some superficial need to do it that way because the software makes it so.
Get some training, start with CAST if you can and any other materials you're able to find from whatever sources are available to you. Install the documentation that comes with the software, you'll find that you can work through the commands and by hitting F1 get some explanation of how each is used. That explanation may only be sufficient to indicate to you whether you feel it will be useful to study that function further, but take the opportunity to look at the whole of what is available to you in modeling if only briefly in order to gain a sense of how the system is designed. In NX-4 you may need you select an advanced role to ensure you have a good look around, but later a beginner would probably stick with the basic role as it suggests ways that the system is best tailored towards.
Try to get some training from a proper trainer either through UGS/PLMS or another reputable provider. You need to alternate training with real world problem solving so don't do all the training in one hit. You need to use it or lose it so to speak. If you aren't lucky enough to get face to face training then try
an online course is better than just CAST and worth it on that basis, which is to say they're not overly expensive.
Be scientific and experiment ALOT, those things which you learn of your own devices stay with you forever. You own those ideas. Start simple and really basic to prove that something works before you contrive to attempt the test case which you suspect may fail. That sort of thing helps.
Best Regards
Hudson