Refers to oral sex, where in the act of a blow job the giver "spits" on the knob to help with lubrication. Because of this the knob end tends look shiny and "polished".
This style of blow job is seen in a lot of porn movies.
It is an extention of a guy asking for a "polish", meaning he like oral sex.
"My ex used to give a real good spit and polish"
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