Something like this example may be all you need (I've used a Dictionary rather than a basic collection - more efficient, better type safety):

Imports System.Collections.Generic
Imports System.IO

Namespace ConsoleApplication3
	Class Program
		Private Shared Sub Main(args As String())
			Dim userA = New User() With { _
				Key .Name = "Gary", _
				Key .OperatorName = "Gary NiceGuy", _
				Key .ID = "Gary", _
				Key .AccessLevel = 4, _
				Key .Password = "50564348" _
			}
			Dim userB = New User() With { _
				Key .Name = "Tester", _
				Key .OperatorName = "Tester Hester", _
				Key .ID = "Tester", _
				Key .AccessLevel = 1, _
				Key .Password = "435242455243" _
			}
			Dim users = New Users()
			users.Add(userA.Name, userA)
			users.Add(userB.Name, userB)

			Using sw As New StreamWriter("test.ini")
				For Each v As var In users
					sw.WriteLine("[" & v.Key & "]")
					sw.WriteLine("OperatorID=" & v.Value.ID)
					sw.WriteLine("OperatorName=" & v.Value.OperatorName)
					sw.WriteLine("AccessLevel=" & v.Value.AccessLevel.ToString())
					sw.WriteLine("OperatorPassword" & v.Value.Password)
					sw.WriteLine()
				Next
			End Using
		End Sub
	End Class

	Public Class User
		Public Property ID() As String
			Get
				Return m_ID
			End Get
			Set
				m_ID = Value
			End Set
		End Property
		Private m_ID As String
		Public Property Name() As String
			Get
				Return m_Name
			End Get
			Set
				m_Name = Value
			End Set
		End Property
		Private m_Name As String
		Public Property OperatorName() As String
			Get
				Return m_OperatorName
			End Get
			Set
				m_OperatorName = Value
			End Set
		End Property
		Private m_OperatorName As String
		Public Property Password() As String
			Get
				Return m_Password
			End Get
			Set
				m_Password = Value
			End Set
		End Property
		Private m_Password As String
		Public Property LoggedIn() As [Boolean]
			Get
				Return m_LoggedIn
			End Get
			Set
				m_LoggedIn = Value
			End Set
		End Property
		Private m_LoggedIn As [Boolean]
		Public Property AccessLevel() As Integer
			Get
				Return m_AccessLevel
			End Get
			Set
				m_AccessLevel = Value
			End Set
		End Property
		Private m_AccessLevel As Integer
	End Class

	Public Class Users
		Inherits Dictionary(Of String, User)

	End Class
End Namespace