You can use Task Scheduler to run programs at startup with highest privileges.
Task Scheduler - Create Task - Vista Forums
They should start without UAC intervening.
As for programs you run yourself - there is no whitelisting.
May be better to stop UAC prompting admins.
User Account Control (UAC) - Elevate Privilege Level - Vista Forums
[HKEY_LOCAL_MACHINE\SOFTWARE\Microsoft\Windows\CurrentVersion\Policies\System]
"ConsentPromptBehaviorAdmin"=dword:00000000
To restore to default:
[HKEY_LOCAL_MACHINE\SOFTWARE\Microsoft\Windows\CurrentVersion\Policies\System]
"ConsentPromptBehaviorAdmin"=dword:00000002