Is there any official document that can guarantee that adding a column to a SQL Server table referenced by EF6 in an existing system will not affect the system?
Are you saying that you have an existing application which uses EF6 to do some operation of the existing database table and you want to add a filed to the existing database table?
If so, I believe that there is no such official document. It is not possible for anybody to guarantee since nobody knows your details (i.e., schema of table, added field, usage of table in your application).
Can you tell us the details? For example (only example though, please write your case),
(1) Entity Data Model was created using the Visual Studio based on the Microsoft sample database Northwind (probably everybody knows its schema):
(2) Controller and views of ASP.NET MVC5 were created for CRUD operations of the Products table using ASP.NET scaffolding available in Visual studio.
(3) You want add field [Remark], nvarchar(255), NOT NULL.
(4) Your question: above (3) affects the CRUD operation of the MVC5 application?