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It would step it down... if you put ddr400 in a slot that only supports up to ddr333, the board will just clock the ram down to 333. Whether or not you can overclock is somthing that is dependant upon the board you buy, the quality of ram used and a little bit of luck. And yes, it really is overclocking, at least from the motherboards' standpoint. Your RAM may be able to run faster but that doesn't mean that you won't fry memory controller or burn up your bus by making it run faster/hotter then it's rated for.
I've already lost a motherboard and 2 videocards due to overclocking... they're expensive lessons to learn. Make sure before you embark on any overclocking stint that you have both a good cooling solution for your case and good clean power (that means a UPS not just a $5 power strip).
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