As Pete mentioned, the primary purpose of tetraethyl lead was to control knock by altering the rate of burn of the fuel molecules.
The notion of the lead as a "lubricant" is pretty much fictional, or to be more charitable a misinterpretation. The former Union Oil Co. did exhaustive (pun intended) analysis and produced an SAE paper defining the unintended positive outcome for exhaust valve life, as did others. The lead additive was disolved in solution, that's why you never had lead balls or film at the bottom of your tank. In the combustion process the lead became oxidized and it was a portion of that lead oxide that "plated out" on the exhaust valve (obviously wouldn't affect intake because it was still in solution when it went past that) and seat on it's way out. As those of you who are familiar with welding have learned, it's difficult to weld dirty (as well as dissimilar) metals. Because of the high heat (under certain extreme operating conditions) the exhaust valve endured it would form microscopic welds from valve face to seat that were broken as the valve opened. Over time those breaks accumulated to be recognized as valve/seat erosion. The lead oxide had the effect of dirtying the valve/seat interface preventing welding.