Is there an alternative to string.Replace that is case-insensitive?

Seems like string.Replace should have an overload that takes a StringComparison argument. Since it doesn't, you could try something like this:

public static string ReplaceString(string str, string oldValue, string newValue, StringComparison comparison)
{
    StringBuilder sb = new StringBuilder();

    int previousIndex = 0;
    int index = str.IndexOf(oldValue, comparison);
    while (index != -1)
    {
        sb.Append(str.Substring(previousIndex, index - previousIndex));
        sb.Append(newValue);
        index += oldValue.Length;

        previousIndex = index;
        index = str.IndexOf(oldValue, index, comparison);
    }
    sb.Append(str.Substring(previousIndex));

    return sb.ToString();
}

From MSDN
$0 - "Substitutes the last substring matched by group number number (decimal)."

In .NET Regular expressions group 0 is always the entire match. For a literal $ you need to

string value = Regex.Replace("%PolicyAmount%", "%PolicyAmount%", @"$$0", RegexOptions.IgnoreCase);