Yeah, what you can do is open Activity Monitor and check actual RAM usage.
Even if your Calistoga (that's the chipset not Napa, Napa is the Centrino platform) MBP reports the full 4GB you can see your system is using a lot less.
Addressable RAM = Used RAM + Free RAM
where Used RAM = Wired RAM + Active RAM + Inactive RAM
Check Activity Monitor for those figures and add the numbers. In a Calistoga MBP like the OP's, you'll see that the total is 3GB which is the addressing limit. Although the MBP sees it's installed, that last GB is simply not available to the OS.
The performance advantage of having a 2nd 2GB DIMM rather than a 1GB DIMM comes from dual-channel memory access. However only very few tasks are bottlenecked by raw FSB bandwidth. A good example where people see a benefit from the matched DIMMs are MBs with integrated graphics where all the communication between the GPU and the video memory (which is actually in regular RAM) has to go over the FSB. In such a situation you can see roughly 15% performance advantage for matched DIMMs. On a MBP there is dedicated VRAM so this bottleneck doesn't exists and the performance advantage of matched DIMMs is almost zero.
If you get a good deal on a 2GB DIMM (like the OP did) 4GB certainly won't hurt. OTOH if you can get a 1GB DIMM easier or for less, there's no reason to go for a 2GB instead. There's more information
in this discussion here.