When it comes to TV, I find that PLIIx gives me a better feeling of being surrounded by the sound, with better detail and better highs/lows. With two-channel DVDs such as TV shows sound great with PLIIx. Of course, all of that could be just my imagination. My ears are far from golden, and it's tough because the two (PLIIx and Neo:6) do sound very similar.
Strangely, I find that when I try either PLIIx or Neo:6 with stuff I've taped on the VCR, everything comes out the centre channel. There's absolutely no information coming out the mains nor the surrounds. So I usually just leave it on 7 channel stereo mode for VCR stuff.
With DVDs that are in 5.1, for some reason, I'm unable to switch to PLIIx or Neo:6. The option is just not present on my receiver when I try to enable it. It's not that big a deal for me, though.
cheers,
supervij