I am not sure if this is all of your code, but you are missing a flag that tells whether a room is reserved or not. Start by declaring
Dim reserved As Boolean = False
Then, at the end of your btnReserve Sub, you add
HotelArray(intRowNumber, intColumnNumber).reserved = True
Also, before you declare a room as "reserved", you will have to check to make sure that it is not already reserved.
If HotelArray(intRowNumber, intColumnNumber).reserved = True Then
MessageBox.Show("This room is reserved.", "SORRY!", MessageBoxButtons.OK, MessageBoxIcon.Information)
Exit Sub
End If
...or some variation of that.