VOR-DME 15 at KMTN is a classic. Not sure if it's even still around.
There's a VOR-A I think into KBTM that killed an Amflight crew a few years ago because they forgot to turn 15 degrees or so crossing the VOR, that's one worth doing in the sim.
LDA approaches into KASE and KTVL are cool. Really any approach in Alaska, for example the LDA 8 into PAJN, or some of the approaches into PAKT...expectantly if your sim models terrain and you set the vis to what the student will think of as VFR-3ish miles and 2000' ceilings. Then when the approach dumps them 4 miles from the field in crummy weather with terrain things get interesting.
LDA approaches can be hard to do though because a lot of sims don't model them accurately-they assume the LDA is on the runway and/or aligned with runway heading, which as I'm sure you know they are not, or they would not be LDAs.