Cache is actually RAM (memory) dedicated to a particular use, and extra - NOT part of your computer's RAM. From your post, I'm sure you are talking about cache on a hard drive (HDD), and that's on the printed circuit board of the HDD itself. It is used for temporary storage of data going to and from the HDD platters, and it's all managed by the HDD unit so it's virtually "invisible" to the computer. Windows knows nothing about it - the HDD just works.
Yes, 64 MB of cache is much better than 16 MB on a HDD. It makes data access on the drive faster. In general, 16 MB is the minimum you want to have, 32 MB is significantly better, and 64 MB is a bit better than 32.