Also, I don't hate the Green Arrow/Black Canary pairing as much as some, but am I totally off base in thinking that she seems to have more chemistry with just about EVERYONE (male and female) else?
Yes, but that makes sense for Year One.
This has changed somewhat following Green Arrow: Year One, but originally Ollie's motivation in being a hero was an even mix of staving off boredom and trying to help people. He was a cocky jerk who was trying to make a name for himself and he rubbed EVERYONE the wrong way. He was still basically a decent guy who wanted to do good but he was still a cocky jerk.
It wasn't until later - after his company was Enroned out form under him - that Ollie began actively trying to be a nicer person AND a better person and that was when Dinah realized there was a nice guy trying to get out of the pompous jerk.
According to the last Black Canary mini, that seems to have been stepped up a bit and both Dinah and Ollie were recruited into the JLA at the same time and it was on their first mission together that Dinah started seeing signs of the Ollie she fell for.
That being said, I wish it was still in continuity that Ollie was secretly funding the JLA from day one. That was an utterly awesome idea on Waid's part and totally fits Ollie to a T.