Well, my team consist of Mai, Kyo and Daimon, when it comes to Neo Maxes though, it's tough since you constantly have to watch the meter and often times I end up using the HD meter for cancels when I'm in a tough spot, and since Neo's are the s most costly type of move in the game; it's tough to manage when to use it or not.
As for Neo Cancels, I'd say your best bet is to use it while on the offensive, I try not to block which isn't really recommended when attempting since you won't be able to properly perform one, although this property can be turned into a useful Option-Select by buffering a (EX) Special Move behind other Specials. If the first special is blocked or whiffed then it will not be Drive Canceled. If the opponent is hit, then the buffered Drive Cancel will automatically activate and hit the opponent, I typically use this and apply it to make frame traps more damaging or to make low-damaging approaches stronger, in my case when I use Mai, I use the Musasabi no Mai (Air + ) move against an opponent and then input Musasabi no Mai (Air + + ) which results in two outcomes which either my initial dive could be blocked by the opponent or whiff due to spacing in which Mai would recover from the dive as normal, or on hit Mai would Drive Cancel her first dive into her dive which allows for a juggle followup, it a little tough but I'm getting the hang of it, I haven't tested it with Yuri, although it shouldn't be too tough if you manage to properly apply it and manage your Neo gauge.
Some Neo Maxes are really good which result in great fullscreen punishes for projectiles (Kyo, Maxima), which are kind of hard to pull from my experience, some are outstanding anti-airs (Iori, Maxima), some are instant command grabs (Duo Lon, Ash), and some even counter moves (Daimon, Elizabeth). It's tough but I've managed to semi master certain Neo's, one I can certaintly use is Mai's .