| I started with PHP (unless you count HTML haha), but if I could take it back I'd go with Java.
Java has an extremely powerful repository of pre-made code for you to use so you can concentrate on the more difficult aspects of your program. If you run into any problems then the JavaDocs are only a couple of clicks away. Not only that, but you are taught Object Oriented Programming right from the start as opposed to procedural. When I first started, I was like OOP??? Why the hell do you need OOP...humans don't think in this way, it's just a bunch of bs. But now I can't really live without it, and I even use PHP5 for all my PHP scripts now. It's all worth it.
The LANGUAGE isn't all that hard to master, but the true test of a great coder is how well they've mastered the API for optimal efficiencey. Reinventing the wheel is generally frowned upon in Java. In terms of API mastery, I personally feel that I'm nowhere near anything above the newbie level, but I learn something new every day =)
After Java comes C/C++, but there's no reason to go beyond Java if all you want to do is bot Neopets. Also, Java can be run on multiple platforms without the need for finding all those .ocx or .dll files like you would have to in a language like VB. And with IDEs like NetBeans on the horizon, GUI creation couldn't get easier (although I recommend you develop GUIs without an IDE in the beginning.)
DON'T DO VB JUST BECAUSE PEOPLE ARE SAYING IT'S EASY...YOU WILL FUCK YOURSELF OVER IN THE ASS!!! | 
