Other mistake: Samantha is reading a 4-line note from Endora. The paper is semi-transparent and in a shot from the front, we can easily see the writing through the paper. However, after the note is "twitched" into a second, shorter note, there's another shot from the front - and the lettering looks exactly the same as it did before. (00:16:40)
Revealing mistake: When Endora goes to Darrin's workplace and puts the spell on him she appears to be floating. Look closely and you can see the wires holding her up.
Answer: Larry had been telling Darrin what it means psychologically that Samantha gave the coat away. Larry said giving it away meant she's happy being married but if she liked the coat it means she desires to be single and carefree. So when Darrin sees the coat, he immediately thinks Samantha doesn't want to be married and the fact that she twitched it means (in his mind) she wants to be a single, carefree witch again.
Bishop73