I have a magic shield with 23% block chance and +1.81% block chance, and the character sheet shows it correctly at 24.58%. If I instead equip a shield with 18% chance to block and -1.85% increased block chance, instead of 16.15% (or even 19.85% if it added it) I get 20.62% block chance. These items have no other modifiers listed that might affect block chance.
This has happened with every red penalty affix so far. I have 25 intelligence without using a whip with -8 intelligence, and 70 with it.