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Haven't played BW2 nor have I gone through BW1's post-game. Kind of skipped Gen 5.
Cynthia > Blue > Steven > Lance > Wallace > Diantha
Cynthia's the best champion. Design-wise, she looks the part for being champion besides those weird lucario trinkets. Gameplay-wise, she's the most challenging champion. Story-wise, she helps you throughout the story, giving a Togepi egg, and lets you deal with Giratina and Cyrus yourself so you can improve. Total bro. Her music theme ain't half bad, either.
Blue's the second-best. It's implied he was the first Kanto champion, and your match with him serves as a fitting conclusion to your rivalry...curbstoming his team yet again. Oh well, at least he has the best champion theme. The FR/LG remix in particular has this "oh god damn FUCK YOU BLUE I am ending this shit NOW!" feel to it. On the bright side, in FR/LG, the post-game rematch gives him a fucking Tyranitar, more competent movesets, and like 10 extra levels, making him slightly challenging.
Steven's the third-best. He helps you out throughout the game, which is nice, though Cynthia's help was more important (dat Togepi). His design is...okay, I guess. He was easy for me to beat, but I walled his best two Pokemon (Aggron and Metagross) with fuckin' Shedinja, and most people tend to not use that, so, yeah...I beat him in Emerald too, but I was such a cheap bitch about it, I just stuck a Pelipper at the front and used all the x-items that ever existed so he can sweep his team so I wouldn't have to grind. I didn't feel like grinding up ten levels to take down a single trainer.