As a general statement, those are categories of accuracy. There has been some changes in the naming convention for blocks, and I don't believe the letter grades are being produced now.
From Starrett's Webber division:
The B89.1.9 standard became effective in July, 2002. On January 6, 2003, Webber began to sell gage blocks to the new
B89.1.9-2002 standard. The Federal standard, GGG-G-15C, has been withdrawn.
So, the B89 standard is what you will see for sale in catalogs now. Here is a link to the Webber page where the tolerances for each grade and size are given.
http://www.starrett-webber.com/GB40.html
They explain it better than I can. There is also a link to the old standard, for reference.
As far as using them for measurement, they of course aren't used for direct measurement, but as a comparison. You can stack them for use on the surface plate and transfer measurements with a height gage. You can set up a sine plate or sine bar with them. You can setup a fixture to set a bore gage. You can use them to verify a micrometer or caliper. And other things. I believe that every machine shop, whether pro or hobby, should have a set. Unless you have a controlled environment, no point in getting the tight tolerance block set.