Personally, although we dive with Lahaina Divers to Lanai, I would never recommend them to very experienced divers looking to avoid a cattle boat. Although I don't consider them a cattle boat, many do because of the fact they can carry 24 divers, and sometimes do. IMO Lahaina Divers is an excellent choice for the beginning or occasional diver, or anyone who wants a big comfortable boat for the often rough crossing to/from Lanai (which is why we go with them).
If you want to be "guaranteed" to be on a boat with advanced divers, the only operator that I know of who specifically runs charters that cater to the advanced diver is Ed Robinson's Diving Adventures. They have a 3-tank charter on Tuesdays and Fridays, and an Adventure charter on Sundays and Wednesdays. Wednesdays is when Ed will be on the boat if he's on island.
What makes these charters "advanced" is usually the depth and conditions. Most (if not all) of the dives will be live boat dives, so those not comfortable or experienced in doing mid-water safety stops and boarding a boat in rough conditions, shouldn't consider these dives. They also expect the divers to be more independent, and although the dives are led by a DM, the DM is pretty much just there to navigate the site and point out creatures....definitely NOT to babysit.
All that said, Makena Coast Charters, Mike Severns, and B&B are all excellent choices as well for charters leaving out of Kihei.
Additionally, before we bought a condo in Kihei, we used to drive down to Kihei from Kaanapali (West Maui) to catch our boat. It's about a 45 minute drive and for us it was worth every minute of the trip. The boat ride out to Molokini is short from the Kihei boat ramp, and South Maui sites have never disappointed.
One amazing thing nobody has mentioned is that February is the uber-high time for Whales in Hawaii! So you'll not only be treated to whale watching on the surface, but you're pretty much guaranteed to hear whale song during your dives. If you're very lucky, you may ever see one underwater!!
I will also add (to this long post) that if you don't want to get up early to catch a 6:30am boat, Shaka Doug is the way to go for shore diving. I believe he doesn't start until 9:00am, and I have yet to hear anything negative about him. We haven't had the pleasure of diving with him yet, but I'm thinking next summer...
