Yes, it will do fun things like turn 1.0f + 1.0f into (1.0f,0,0,0) + (1.0f,0,0,0), that is better than having to deal with the old floating point stack, but doesn't really exploit the full potential of SSE instructions.
These will be used by default (at O2 without vectorization enabled) for single-precision floating point math on x86-64 (where stack-based FPU is deprecated).
Vector instructions you're referring to end with "ps", they're very unlikely to be emitted for typical fp operations.