Depends on your tastes. If you disregard Al's first album "With Sympathy" as a straight synth-pop album that the label supposedly controlled then "Twitch" and "Land of Rape and Honey" are both excellent but way more Electronic/Industrial sounding. Their roots are from Wax Trax! Records in Chicago and they really shaped the whole label and scene. They got more into guitars after Paul Barker joined the band around "Mind" and then went all out with it at Psalm 69. Both of which are really great albums. I also really love Filth Pig which came out after it but it was not as well received and it is a bit slower and more doomy than their previous albums. So if you prefer more "synths" go with Twitch and LORAH, but if you are more into guitars go with Mind or their most popular album Psalm 69 (the Jesus Built my Hotrod single sold over a million copies). All of those albums have great moments. But I would definitely start with any of these as it was their strongest output. I used to run their official website back in the day and really love the band and have seen them countless times. Glad this album is finally easier to get.
Check out these songs on youtube for an idea of how they progressed: We Believe, Land of Rape and Honey, So What, Thieves, N.W.O, Just One Fix, Lava. And then listen to "Everyday is Halloween" just for fun.