Kanno Primer
 

I'm looking to get into some Yoko Kanno and I need some help.

Context: The only Kanno soundtrack I have is that gussied up Uncharted Waters II Special Edition soundtrack (which I decently enjoy). Most of my exposure has come from tracks in SotW and BSC. As a template, favorite tracks of hers include Southern Twilight ~ Dance on a Cape of Good Hope from UWII, Wild Wind from Napple Tale Vol. 2 and Blue Whitecaps from Nobunaga's Ambition: Haouden.

Overly cute or saccharine is not my thing.

So soundtracks do you suggest I check out first?

All of them, you poor bastard.

First, the Ragnarok Online II soundtrack. Then we start with her anime scores. Specifically, the Kiseki no Umi single from Record of Lodoss War TV, because that is hands down the best vocal song she has ever written. (The actual soundtracks are by Kaoru Wada though, so ignore those)

After that, I dunno, try Please Save My Earth, Brain Powerd, Macross Plus, Escaflowne (3 albums plus a movie soundtrack) and RahXephon (another 3 albums and a move soundtrack), just to start. Then try out her most famous anime music work: Cowboy Bebop (3 albums plus a movie soundtrack -- are you seeing a pattern here yet -- plus supplementary vocal albums) and Ghost in the Shell: Stand Alone Complex (6 soundtrack albums in a boxset). I really like the songs in Wolf's Rain, too. You'd probably like it too because it's one bloody depressing soundtrack.

Then you can try Macross Frontier (2 albums plus singles) to get up to speed.

Yeah, what Bigblah mentioned is complete enough.
I also recommend her music from Turn A Gundam (my first encounter with Yoko's music), 3 albums plus a movie soundtrack (dam right Bigblah, =)) this IS her pattern). Military Boots, Dark History, God Advent, Tsuki no Mayu, just some of awesome tracks in this series. Try it out!

Not going to lie, I'm going for her VGM stuff first. If I'm enjoying it enough, then I'll slide into her anime selection. But I got enough music on my plate without the need for anime normally.

Kanno hasn't really done anything remarkable in the vgm scene. Apart from The Era of Great Voyages II Special Edition (KECH-1061) and the Napple Tale soundtracks.

Her anime works are a lot more interesting and inspired.

It's the music she made for Koei in the '90s you should focus on then. You can check her VGM discography here. Pretty much all the albums between '89 and '94 not called 'KOEI Original BGM Collection...' are arrange albums in the vein of the Uncharted Waters II SE album you mentioned. A good entry-point could be the five 'The Best of KOEI' compilations, each featuring selected tracks from preceding releases.

These old-school Koei arrange albums are generally held in high regard - and not only Kanno's works - they are pretty much all good.