Vino won on his third day of competition after returning (Stage 3b, 2009 Tour de l'Ain), which beats Valverde (fifth day of competition if we don't count the Cancer Council Classic).
Vino's suspension was lifted on 22/07/09, and he won on 11/08/09, meaning he won a race on his 21st day of eligibility. Valverde's suspension was lifted on 01/01/12 and he won on Old Willunga Hill on 21/01/12, so he managed the same time from suspension to victory.
However, both of them pale in comparison to Alessandro "Ale-Jet" Petacchi, whose suspension for salbutamol ended on August 31, 2008, making him eligible to ride again on September 1 (although to be fair the suspension was mostly backdated; he lost 9 months of results, but was only suspended for 3 months as a result); he won the first stage of the Tour of Britain with his new team, LPR Brakes, on September 7, his first day of racing action and his seventh day of eligibility.