This is what I just did...
1. I typed 0.25 into cell A1
Cell A1 is formatted as "Number" with 2 decimal places.
2. I clicked the percentage button.
Cell A1 now shows "25%" and the cell formatting has changed to "percentage"
(The cat agrees)
Are you saying this does not happen?
I think the problem arises because once you have clicked the percentage button, the format of the cell is changed from number to percentage. If you leave it like that, then type another decimal number in, then you get the result you described. Read Soybean's post again.