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Blocking

The chance to block is determined by comparing the two players' Dexterity. So for example, if you have Player A and Player B:
Scenario 1:
Player A - Dexterity = 20
Player B - Dexterity = 20
Because both players have the same Dexterity, if Player A attacks Player B, Player B's chance to block Player A's attack will use default 15% block chance.
Scenario 2:
Player A - Dexterity = 35
Player B - Dexterity = 20
In this scenario, because Player A has significantly more Dexterity than Player B, when Player A attacks Player B, Player B will have a "below default" chance to block the attack.

Block Calculations

Block is calculated by adding the block chance adjustment to the default block chance (currently 10%).
Block chance = 10% + Block Chance Adjustment
The chance to block can never be less than 4% The chance to block can never be more than 45%
Block Chance Adjustment = (Defender's Dexterity - Attacker's Dexterity) / 2

Example 1:
Defender has 100 Dexterity
Attacker has 60 Dexterity
Block Adjustment = (100 - 60) / 2 = 20
Chance to Block = 10 + 20 = 30%

Example 2:
Defender has 60 Dexterity
Attacker has 100 Dexterity
Block Adjustment = (60 - 100) / 2 = -20
Chance to Block = 10 + -20 = -10%

Since the block chance can never reduce below 4%, the Chance to Block becomes 4% (THIS IS WHY EVEN IF YOU INFINITELY HIGHER DEX THAN THE OTHER, HE/SHE CAN STILL BLOCK (albeit not likely))

Example 3:
Defender has 30 Dexterity (Also, the defender has a -40 Dexterity Debuff Applied)
Attacker has 29 Dexterity
Dexterity never uses negative values in calculations ... so even though a debuff is applied, the Defender's dexterity value is calculated using the minimum value of 1 instead of -10.
Block Adjustment = (1 - 29) / 2 = -14
Chance to Block = 10 + -14 = -4%
Since the block chance can never reduce below 4%, the Chance to Block becomes 4%

A good rule of thumb is that for every 2 points of Dexterity you have more or less than your enemy, your chance to block increases or decreases by 1% respectively.