Perfume is a highly versatile and can be applied to the neck, wrist, armpits, decollate, navel, hair and feet. You will want to avoid applying it to the face and any mucous membranes.
Best time to apply perfume? Any time is a good time, but after showering is best, while the skin is still warm and allows the fragrance to settle nicely.
Perfume mists can are most traditionally applied at the wrist, or chest or misted into the air and walking into said mist.
Oils can be applied by tipping the bottle directly to the skin, or dabbing a bit on the finger and applying where you like. You will not ruin your perfume oil if you touch it.