silicone will not hold paint so if this sill is painted and you apply silcone, next time you paint it will just never stick to the area that silicone touches, this will be a big problem espically if your changeing colors.
silicone will also crack, grow mold and change color, this problems are coumpounded in wet damp areaars such as showers
you could try it but i wont recomend it. i have not used silicone chaulk in years because odf these problems