Ok, so I found this picture done by Tite and it shows all of the previous captains and lieutenants 100 years ago. Now most of you guys wont know who some of these people are, I mean I had no idea until I checked on the Bleach Wiki page but I thought it would be cool to draw. I also don't know if it's considered spoilers or not since most of the characters everyone knows and the others no one knows about. Anyway, I'll list off their names from right to left.

Genryūsai Shigekuni Yamamoto - 1st Captain
Chōjirō Sasakibe - Lieutenant

Rōjūrō Ōtoribashi(a.k.a Rose) - 3rd Captain
Chikane Iba (I have no idea who she is) - Lieutenant

Shinji Hirako - 5th Captain
Sōsuke Aizen - Lieutenant

Love Aikawa - 7th Captain
Jin'emon Kotsubaki (Got nothin on this guy neither) - Lieutenant

Kensei Muguruma (My favorite Visored) - 9th Captain
Mashiro Kuna (She's super funny!) - Lieutenant

Kisuke Urahara - 12th Captain
Hiyori Sarugaki - Lieutenant

Yoruichi Shihōin - 2nd Captain
Marenoshin Ōmaeda (Marechiyo Ōmaeda's dad) - Lieutenant

Retsu Unohana - 4th Captain
Seinosuke Yamada (No info really on him either) - Lieutenant

Ginrei Kuchiki (Byakuya's grandfather) - 6th Captain
Sōjun Kuchiki (Obviously a Kuchiki, maybe Byakuya's dad?) - Lieutenant

Shunsui Kyōraku - 8th Captain
Lisa Yadōmaru - Lieutenant

Kenpachi Kiganjō (Killed by Zaraki) - 11th Captain
Apparently no Lieutenant

Jūshirō Ukitake - 13th Captain
Not sure who his old Lieutenant was. I'd assume it was Kaien but This person looks to be wearing a long collard shirt, not something Kaien wore.

I'm really sorry guys, I really butchered some of their faces and I will expect some ridicule on that.
Anyways, remember to hug, favorite, comment and subscribe! I really like comments!