Nope, the caches are not added together that way unfortunately, for all intents and purposes it will only use 8meg on each drive. The difference between 8 and 16 isn't that significant to warrant a new drive purchase so I wouldn't bother. For an example, my raid controller has 128megs of cache and if I disable it i don't notice much of a difference under normal usage.
Long story short, you're just fine with an 8 and a 16
Though if your data is important I'd reccomend doing a RAID 0 on the two 16's and using the 8 as a backup. I know I tend to over-stress this in my posts but I've lost a lot of data, remember if either drive fails all data is lost, if the board/controller dies all data is most likely lost depending on the situation, drives fall out of arrays etc.