I just purchased a 5-disc player, and, yes, you can program it to play different titles and chapters from different DVDs. It takes a little longer for my player to switch DVDs than it does to skip chapters and titles on the same DVD. Still, at most, it takes about 10 seconds to skip DVDs, and the player goes right to the chapter and title I've programmed. I haven't found these skips overly disruptive.
I got a smoking deal on my disc player in a one-day-only-4th-of-July sale and haven't regretted for one second my purchase. It has all kinds of fancy features, many of which I have yet to explore (but hope to soon).
If one of your primary reasons for purchasing a 5-disc player is to program Cathe DVDs, I would suggest taking a couple (along with their Chapter & Title information) to the electronics store and asking someone to let you try programming the players you're interested in. When I went to purchase mine, none of the store employees knew off the top of their head if the players could be programmed. I ended up asking for the instruction booklet for the player I wanted and testing it for myself. That way, I found a player that I knew had the features I wanted.