Seeing Ron Mael staring into the camera on Top of the Pops whilst playing "This Town Ain't Big Enough..." with Sparks is without doubt my most vivid early childhood TV/music memory.
Other strong TOTP memories were the first time Slade's "Merry Christmas Everybody" charted and that Womble record.
On a non-musical note I can remember being gutted when Jo Grant left Doctor Who and then doubly gutted when Jon Pertwee did shortly after :D