As I'm not a Java programmer, I'm curious as to why this is better? Does the other method actually do the bitwise operation math to determine the endian, and this method just pull a value?
It is a very simple principle: If you want a question answered, you should ask exactly the right question. The original poster wanted to know if Java is running on a PowerPC or an Intel chip - and that is what the code checks. Run the same code on an ARM chip and it will give the correct answer: It is not running on a PowerPC chip and not on an Intel chip.
The other code told you that Java was running on a bigendian or littleendian machine. You can draw conclusions from this, for example whether you are running on PowerPC or Intel. Run the code on an ARM chip, and the conclusion will be wrong.
(I bet that there is lots of code that was supposed to run on either Windows or Macintosh, but checked for Intel vs. PowerPC instead. Probably was fun fixing all that code for Intel Macs. Don't make assumptions. One day your assumptions will be wrong).