Board Thread:Questions and Answers/@comment-6057702-20130727135327/@comment-8986886-20130727220006

Kisuke mastered Hakuda in the Maggots Nest, he uses Kidõ of the 90's level, was quick enough to place seals on Aizen's wrists (Shunpo) and later held his own against him when they drew their Zanpakutõ (Zanjutsu)

And I think the "old" generation of Shinigami captains; Yamajii, Unohana, Shunsui and Ukitake, probably mastered the four basic fighting styles over the centuries; we simply haven't seen them use it all.