There are a few issues at play, here.
As others have said, sometimes the Finder won't acknowledge the full size of a CD. I just don't use the Finder to burn CDs if I can avoid it. I use Toast, or
YuBurner (free), or
Firestarter FX (also free). None of them have ever given me problems, and they all let me fill every bit of that 702.8MB. If you have sufficient privileges, try downloading one of those apps.
The issue with CDs and DVDs is a little different, though. DVDs
do not hold 4.7GB of data! At least not by software standards. The confusion comes from the two different definitions of KB/MB/GB. In hard drive sizes, "GB" almost always means "one billion bytes" (decimal counting). But all software defines a GB as 2^30 bytes (binary counting; that's 1,073,741,820). CDs are measured using binary counting. DVDs are not, for some annoying reason.
Therefore, a DVD's "4.7GB" = 4,700,000,000 bytes = 4.377 GB by software standards.
Another factor to consider is formatting size. The invisible HFS+ database files can be quite large on volumes with many files. I don't think that could account for the ~100MB of missing space you're getting on your DVD, though.