The primary toxin excreted through the skin is urea, but this is not urea's primary method of elimination. Small amounts of other toxins can also excrete through the skin such as nicotine, nickel and lead.
Would it speed up detoxing the more we wash our skin and hair?
To an extent. Plugging the pores with sebum, waxes or polymers can inhibit proper excretion of compounds through the skin. Problem is that most people use conditioners, which contain waxes and polymers. And after bathing they often use lotions with waxes and polymers.
You said if we don't wash our hair regularly the oil will slow up. Would that slow up detoxing also?