...because the .NET environment is designed to support many languages.
System.Boolean (in mscorlib.dll) is designed to be used internally by languages to support a boolean datatype. C# uses all lowercase for its keywords, hence 'bool', 'true', and 'false'.
VB.NET however uses standard casing: hence 'Boolean', 'True', and 'False'.
Since the languages have to work together, you couldn't have true.ToString() (C#) giving a different result to True.ToString() (VB.NET). The CLR designers picked the standard CLR casing notation for the ToString() result.
The string representation of the boolean true is defined to be Boolean.TrueString.
(There's a similar case with System.String: C# presents it as the 'string' type).