In the episode where Homer buys Lisa a horse, Lisa is riding the horse and some kids are watching her. One kid says to Ralph "She tamed that horse well" or something like that. Then Ralph says "But what man could tame her" or something. But when Ralph talks, it's in Nelson's voice!
This is NOT a slip-up...this episode was made before Ralph had ever spoken in that voice we all know and love. It's not Nelson's voice either, just very close since it's probably the same voice-over person.
Both Nelson and Ralph are voiced by Nancy Cartwright.
Ralph is a good example of a character that was originally just a random background school kid that eventually became a larger part of the show. For example, when he was introduced he was not yet a Wiggum. I don't think he was established enough at the time this episode was made to really consider it a slip up. I think Nancy just changed the voice somewhat as time wore on. Many of the characters (most notably Homer) have gone through some voice changes as the series has worn on.
In such a long running animated series, you're bound to see characters that either develop into something a little different in order to better suit the needs of the show (think of it as the cartoon version of switching actors) or background/incidental characters that look very similar to characters that are later introduced or characters that sound very similar. The animators can only come up with so many faces and the voice talent has their limits as well.
Look, it's a JOKE. The scene was played for laughs. They were making fun of Ralph's voice by giving it a deeper more *ahem* romantic tone. If you don't realize that, then you people shouldn't watch the Simpsons.