It changes the rate of protein denaturation and starch gelatinization.
Starch gelatinization is when the starch molecule expand with heat as they absorbs the free water molecules in the batter or dough. They eventually become saturated and burst. While this is happening, the dough is stretching and expanding from the the gas created by the leavening.
When the starch molecules burst, they begin to coagulate and set a structure around the gas bubbles creating the porous structure.
Starch gelatinization happens with all flours. But bleached cake slows the rate of starch gelatinization which allows for more rise time.
Protein denaturation reduces the strength and extensibility in the flour. Heat causes protein denaturalization so the temperature in which it occurs is important. Cake flour is low protein, so already weaker flour. The bleaching cause a higher denaturation temperature, so it gives the cake batter more time to rise. Once that peak hits, then the extended starch gelatinization has happened and the batter sets.
So bleached cake flour produces a fluffy, taller cake than pastry flour and all purpose flour. In fact angel food cake can only be made with bleached cake flour. Any other flour and the angel food cake will collapse or be a gummy dense mess.
Bleaching actually happens naturally with oxidation as flour ages. But mills can’t afford to wait for bleaching to occur, they need to sell their flour. So they chemically bleach it.
Where bleaching is prohibited, cake flour is high heat treated to trigger some starch gelatinization and protein denaturation.
Despite all those blogs claiming you can make cake flour by mixing cornstarch and all purpose flour, it not true. You have to understand the science of bleaching flour. And it has nothing to do with adding more starch or a hygroscopic starch to flour.
Cornstarch is a thickener. Cornstarch is so incredibly hygroscopic it creates the opposite texture in cake. Instead of a light airy cake that rises high, the cornstarch sucks up all the moisture and turns thick and gummy. Cornstarch does the opposite of what is desired in cake. And it’s because cake batter contains liquid—significant free water molecules just waiting to bind with the cornstarch. It’s one thing to add some cornstarch to shortbread dough where there’s almost no free water molecules. Quite another to add it to cake batter where there’s significant free water molecules.
http://www.icef11.org/content/papers/epf/EPF493.pdf
https://www.sciencedirect.com/science/article/pii/S0308814696002610