Scenario : As per the business requirement there will be a Picklist values in the VF page from which user can transform the Whole page in his preferred language.
Please let me know if we can handle this type of scenario.
There's no native way to do it. You will have query for those Custom Settings (preferably using Custom Settings methods like .getAll()) and transform them into correct Type - SelectOption.
See this documentation page for tips on how to use Visualforce's and Apex's SelectOption.