Well, the ideal waterblock shape (since the typical peltier module that you would be dealing with is square shaped) is something along the lines of a block shaped like a Danger Den Maze4 GPU form. Now I know that is a GPU waterblock - I just wanted to give you the idea that it should be square shaped like that. In most Peltier waterblocks, you will be dealing with peltier modules that are 40mm * 40mm or 50mm * 50mm in size. 40mm modules aren't going to be of much use to you for CPU cooling because their extreme potential isn't that high (the best I've seen is around 172 to 180 watts perhaps). 50mm modules, thoughh, are ideal as they can get quite high (the module in my Swiftech waterblock is a 226w TEC. There was a company called Arctic Web (which has since gone out of business) that made a TEC waterblock that used a 62mm * 62mm module and was a 437watt unit - very extreme.
Anyway, I hope this gives you food for thought - 40mm * 40mm square is really undersized for CPUs and 50mm * 50mm is just right. So, you take those dimensions when choosing a waterblock. Of course, there is nothing to say that you have to stick straight to the waterblocks that are sold. You can custom make your own block with materials of several blocks if you can find them. On my new Abit board, there is a heatsink near the CPU that cools pwm3 & pwm4 and I am using a GPU waterblock variation to cool them. So, if there is a need, there is a way.
However, the Swiftech TEC waterblock is pretty much the best all around waterblock design right now to use as a TEC/waterblock as it was designed to cool a 50mm * 50mm module. That particular TEC/waterblock costs about $120. Keep in mind of the voltage of the module you are using though. TEC modules that you will most likely encounter will either be 12v or 24v modules and if you are going to use a dedicated secondary PSU then make sure that it is a 12v or 24v corresponding one. Also, a module is always going to be "under-rated". That is, take a 226 watt module. The 12v model of that is actually capable of up to somehting like 15.4 colts so it has an even greater potwntial than 226 watts. The same goes for the 24v variation of the module. Meanwell PSUs that are typically used in TEC setups are designed the same way. I use a 600 SE12 PSU for my TEC and it is rated at 12 volts but can actually raise the voltages up to 15.4 or so. I think you get the picture here. If you could get a voltage adjuster installed for a dedicated secondary PSU that would be ideal (I know a guy who can do that) as it would allow you to raise or lower the power of the TEC based on what you need it for. I have a voltage adjuster on my Meanwell 600 SE12.