The difference between buffers and cache
Buffers are associated with a specific block device, and cover caching of filesystem metadata as well as tracking in-flight pages. The cache only contains parked file data. That is, the buffers remember what's in directories, what file permissions are, and keep track of what memory is being written from or read to for a particular block device. The cache only contains the contents of the files themselves.
Corrections and additions to this section welcome; I've done a bit of guesswork based on tracing how /proc/meminfo is produced to arrive at these conclusions.