I remember the last episode of whatever came before it (Mashed perhaps?) and they did a link up with Ant & Dec at the studios. As has already been said, the focus then was CD:UK, with the selling point being the 'Saturday Chart'.
Although the "Saturday Chart" was hadly new, as The Chart Show had been using it for years, though CD:UK did push how you could og out that day and buy records to influence the final chart the following day. The first few shows had OBs from a record store finding out what people were buying, though it didn't last long.
Someone uploaded the first SM:TV/CD:UK to YouTube a few years ago (though annoyingly cropped to 16:9) and one notable thing was as it was Michael Jackson's 40th birthday they had an MJ themed competition. The question was "what was Michael Jackson's most recent number one", with three options- Black or White, Earth Song and You Are Not Alone. A shame the actual answer was Blood on the Dancefloor.
Funnily enough the first "all new Top Of The Pops" 5 years later made a very similar mistake with Robbie Williams, only the question was about his first number one rather than his most recent- but again the correct answer wasn't one of the choices!
CD:UK did distinguish itself from TOTP with all the features and stuff though TOTP did start to try and copy them a few years later (at first towards the end of Cowey's era, then the dreadful Andi Peters revamp), only it really didn't work there at all. The shorter running time of TOTP didn't help as it ate away into performance time, but it was done badly regardless.