As near as I can tell, it's only one thing. Overclocking.
The older one ran 100 only, could go as high as 105 to maybe barely 110 before you couldn't boot. The newer A runs at either 100 or 133 depending on your chip. What's cool is that you can a 100 Athlon and lower the multiplier and run it at 133. Overall chip speed is the same, but the system runs that much faster. It's a big difference.
If you want a simple easy to do and cheaper PC, the old chipset is fine. If you want the newest, or want a 266 FSB C Athlon, or like to overclock, then you MUST get the 133A on your next board.