If you have a 256MB stick and 512MB stick of RAM in your machine, there is no way they can be matched - both RAM modules have to be the same size - like 512MB & 512MB, 1GB & 1GB, etc.
I'm not sure if I understand your last part. At any rate, running a machine with 768MB of RAM will be better than 512MB, whether matched or not.
If you want to get the best performance possible, either get rid of 256MB chip and purchase another 512MB chip or purchase two 1GB chips.