The easiest way to access the first element of a list is List.head. Since you have a list of lists, you just need List.mapto execute this function:
let listOfLists = [ [1;2;3;4;5]; [6;7;8;9;10]; [11;12;13;14;15] ]
listOfLists
|> List.map List.head
, , List.item xs.[1]. , , , .
listOfLists
|> List.map (List.item 1)
:
listOfLists
|> List.map (fun x -> x.[1])