http://www.uesp.net/wiki/Skyrim:Block has details of the block skill. With no perks a shield will block 45% of damage while a weapon or torch will block 30%. With all the perks and some fortify Block items it looks like it would be possible to get both shields and weapons to the 85% cap though.
See post #4 of this thread for full details:
http://www.gamesas.com/topic/1342463-complete-character-design-freedom-damage-resist-caps-and-ridiculous-damage-thread-10/