If you want to determine what character you will get from a given key with given modifiers, you should use the user32 ToAscii function. Or ToAsciiEx if you want to use a keyboard layout other then the current one.
using System.Runtime.InteropServices;
public static class User32Interop
{
  public static char ToAscii(Keys key, Keys modifiers)
  {
    var outputBuilder = new StringBuilder(2);
    int result = ToAscii((uint)key, 0, GetKeyState(modifiers),
                         outputBuilder, 0);
    if (result == 1)
      return outputBuilder[0];
    else
      throw new Exception("Invalid key");
  }
  private const byte HighBit = 0x80;
  private static byte[] GetKeyState(Keys modifiers)
  {
    var keyState = new byte[256];
    foreach (Keys key in Enum.GetValues(typeof(Keys)))
    {
      if ((modifiers & key) == key)
      {
        keyState[(int)key] = HighBit;
      }
    }
    return keyState;
  }
  [DllImport("user32.dll")]
  private static extern int ToAscii(uint uVirtKey, uint uScanCode,
                                    byte[] lpKeyState,
                                    [Out] StringBuilder lpChar,
                                    uint uFlags);
}
You can now use it like this:
char c = User32Interop.ToAscii(Keys.D3, Keys.ShiftKey); // = '#'
If you need more than one modifier, just or them. Keys.ShiftKey | Keys.AltKey