Many acrostic piyutim interchange ס with שׂ because of their sound being the same. I suppose it is because the author could not find a fitting word that began with ס. One example of this would be in the prayer "L'chai Olamim", in which the line for ס goes:
.הַסִּגּוּי וְהַשֶּֽׂגֶב לְחַי עוֹלָמִים
Also in the prayer "Kel Adon" on Shabbat, the line for ס is replaced with a שׂ:
.שְׂמֵחִים בְּצֵאתָם וְשָׂשִׂים בְּבוֹאָם
These are just two examples, but it seems that it is quite common in acrostic prayers. So Vidui is not the only prayer which replaces ס with a שׂ in the acrostic.