the xp's aren't "266mhz" chips. they are designed to run on a 133mhz DDR system bus (front side bus). however, increasing the bus speed to 166mhz DDR (333mhz) means the chips can be fed information faster and thus they are transformed in "333mhz chips". the Kt333 chipset is supposed to proivde a stable base for systems even when overlocking your processor (from the 266mhz to 333mhz). the upcoming KT400 boards are...well were...supposed to give a way for the system bus to operate at 400mhz (200mhz ddr). VIA is unforuantely leaving it up to the mobo manufacturers to implement the 400 mhz bus correctly, so the key here is buy a quality mobo (asus, epox, abit, MSI, DFI, soyo to name a few). the next step is to get memory that will run at the desired system speed. pc2100 runs at 266mhz, pc2700 runs at 333mhz, and pc3200 runs at 400mhz - price increases as speed goes up. again, name brand quality modules will be faster, more stable, and more reliable than generic. finally, you need a processor that can handle the higher bus speeds. to understand this you need to realize that two things determine proc speed: multiplier and bus speed. the multiplier is exactly that, it multiplies the bus speed to ascertain the processor speed. the bus speed has already been discussed. so if we leave the multiplier alone, and simply increase the system bus...the cpu operates faster in additon to receiving data faster. the only problem is the ability of the core of the processor to handle the extra speed. this is overclocking. the "266mhz athlons" are less likely to be able to run at 400mhz (i've not heard of many that did), but most can reliably work at 333mhz - without lowering the multiplier. the "333mhz athlons" stand a much better chance of attaining "400mhz athlon" speeds - without lowering the multiplier. without going to far in to details on how overclocking affects the rest of the system - that is a pretty decent explanation of why we would use the KT400.
edit: i know i got pretty basic there - didnt mean to insult anyone's intelligence, but i've always found its better to overexplain rather than not explain at all