To become a super user, you need to become accustom to understanding the problems and the pieces that you don't understand. Key to this is understanding differences in environments.
Practice and experience are huge keys to becoming more proficient overall, but they must be coupled with a desire to understand the problems. If you edited a configuration file and it didn't behave the way you expected it to, you need to dig into why it didn't work. Simply shooting in the dark and tweaking it until it magically works will not improve your ability to understand things in the future.
The other key is to understand that computers behave differently based on their environment. Environment in this case means the OS, the OS version, and even the applications installed on that OS and their versions.
If you're using Ubuntu 12.04, for example, then you'll want to search for solutions to your problem on Ubuntu 12.04. If you find a solution to a problem but it's being described on Fedora 16, then you'll probably run into problems related to differences in the environment. Finding a solution described on an earlier version of Ubuntu or even Debian (on which Ubuntu was originally built) would yield better luck.
The beautiful thing about working with computers is that 99.9% of of the time, the problem, no matter how much it doesn't make sense, actually has a logical and sensible solution behind it (as opposed to understanding humans, which can actually make no sense at times).
Computers are systems a lot like humans, minus all the illogical emotional stuff (although I'm convinced that even computers very occasionally experience unexplainable emotional issues). Humans that speak the same language work well together (identical operating systems running on the same network, applications built for a specific OS, etc.). Friends that know each other well can operate nicely together (mature applications built for a specific OS generally run more smoothly than ported apps).
The key to becoming a super user lies in understanding all these differences and in being able to identify differences in environments while intuitively knowing which areas you don't understand.
When something doesn't work the way you expect it to, you'll know which areas to investigate based on what you don't know and you'll save time by ignoring the areas you already understand.