Parrying Skill
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For the best results you need at least 80 dexterity. If your dexterity is below 80, your block rate is lowered in proportion to your dexterity. If your dexterity is above 80, your block rate is based on your skill level alone.
To train Parrying, wear a shield and let things attack you. The most common way to gain fast is to head to a farm, attack all the chickens and then drop out of war mode. That way you have plenty of chickens hitting you and your shield, your parrying skill goes up, and you barely take any damage.
You cannot parry unless you are wearing a shield or holding a melee weapon.
Keep in mind that Parrying is tied to Bushido. You get the best blocking results if you have no bushido at all. If you have some bushido, your ability to parry with a shield drops. In exchange, your ability to parry without a shield improves. At very high bushido levels wearing a shield becomes a problem, because your parry rate with a weapon and no shield will be much higher than it is with a shield.
If your Bushido is higher than your Parrying, you will not be able to raise Parrying with a shield. You have to train it with a weapon only.