First off, it's a 2-sided CLV disc with 2 episodes per side. That means that you can't pause the disc to view an individual still frame unless you have a higher-end player with a digital frame buffer. However, since CLV discs can hold 60 minutes per side versus CAV's 30 minutes per side (as was used for the 2-episode Genesis 0:1 ~ 0:14 releases), it's a necessary technical decision.
There are two identical stereo audio tracks: analog and digital. The analog track is mostly there for compatibility with early players that were produced before the introduction of digital audio tracks. As for the digital audio track, I'd recommend selecting it because of its inherently higher quality. Also, you can bitstream uncompressed PCM audio from the digital track to your receiver if you have a late-model LD player with a TOSLINK optical output connected to your audio receiver.
Now for the actual content. As is common, the first things you see are the corporate logo clips as seen below:
Then you've got your opening credits, nothing unusual about them. However, what comes immediately thereafter is really interesting. There's a still frame with no audio showing Eva-01, Ritsuko, Shinji, and Misato that lasts for precisely 10 seconds immediately after the OP credits end. Based on seeing many a raw TV-rip encode of other series in my day, I'd say that most likely this is where the broadcast sponsors' names would have been overlaid via telop, along with a voice-over saying something like "This show is brought to you by the following sponsors" back when the episode was originally televised.
Presumably that part of the production would have been finished off-site at the station, so Gainax's own master used for this release logically wouldn't have the finished sponsor message with the telop and voice-over completed. Of course, that's just my speculation.
OP broadcast sponsor screen:
From there, the original OA version of Episode 21 begins as normal, with no NPC / DC improvements or added scenes to be found. However, when it gets to the episode's Japanese title screen, something is different: The episode's title is duplicated in hiragana within a box inset at the bottom right!
Episode 21 title screen:
The rest of the episode continues as normal, with the episode-specific ED credits using the proper version of "Fly Me to the Moon" followed by the original 15-second next episode preview. After that, there's 2 more curiosities: There's another 10-second broadcast sponsor screen with Eva-01, and then immediately afterwards there's another 5-second still frame showing Shinji along with text saying "Look Forward to Next Time!".
ED broadcast sponsor screen + "Look Forward to Next Time!"
From there it goes on to the OP credits for Episode 22 and follows the same pattern of presentation differences as listed above. When you flip the disc to the other side (or the player does it for you if you have a nicer model), it starts immediately with the OP for Episode 23 (no corporate logos) and continues as previously outlined through the end of Episode 24. After that, you see the King Records logo, and then the standard copyright message.
In short, when Gainax said that they were going to use the TV broadcast version of Episodes 21-24 for this release, they weren't kidding around. It's just about as close to what was actually broadcast in February and March of 1996 as you can get, short of getting a copy of some otaku's VHS recording of the original TV Tokyo airing!