Because the file allocation bitmap is half the size (32KB clusters vs 16KB clusters = less clusters to track in the bitmap = bitmap is half the size).
Therefore there is 'more' space available to actually 'store' files.
That said, each file will be rounded up to the nearest 32KB block, so the space you gain from doing it may be 'lost' in "file slack" later.
With 128KB clusters, every file would be rounded up to the nearest 128KB in size.
For storing files that are exact multiples of clusters (such as 1GB files) this is never a problem, and you're better off using 32KB or 64KB clusters.
IMHO anything larger than 64KB is just wasteful, and anything smaller than 4KB causes too much micro-management of the file allocation bitmap. (2KB...