I believe her opinion of Piccolo throughout most of the series was that she still associated him as the demon king. But during a filler episode of DBZ where Goku/Piccolo/Gohan were training for the Cell Games, she seemingly forgot about that and just treated him as a freeloading guest who needed to earn their keep. After that the anime really didn't have much interactions with the two. They'd be in group scenes, but ChiChi by that point was a walking meme and not a character so her purpose was to yell at people. In the manga Toriyama only remember she exists when it came to Gohan. I can't recall any scenes where they are together (other than the tournament where she, Goku, and Piccolo Jr fought). She did yell at Kuririn about allowing Piccolo steal Gohan after Raditz and that might be the only connection between the two there. To be honest, Toriyama wasn't all that interested in ChiChi other than to do nagging wife / overbearing mom gags. I think the only female characters he actually considered as actual characters was Bulma and MAYBE Number 18 and Videl (both of which he forgot when their usefulness ended - which is why they just sort of became wives to the important characters). So... just Bulma? lol.