In case of Mater-Details:
For increasing the size of the Expand/collapse button:
Enlarge Exapnd/Collapse button of master detail view in xtragrid
master detail expand button size
If you want to change GridView's expand\collapse icon then you can change it by modifying an image of the Grid | PlusMinusEx skin element. Here is a code snippet illustrating how to replace the image with your custom one in a currently applied skin.
Skin skin = GridSkins.GetSkin(DevExpress.LookAndFeel.UserLookAndFeel.Default);
SkinElement element = skin[GridSkins.SkinPlusMinusEx];
element.Image.SetImage(GetNewImage(), Color.Magenta);
LookAndFeelHelper.ForceDefaultLookAndFeelChanged();
You can also paint the expand/collapse button on the CustomDrawCell event handler. Please see the How to paint the master row's expand buttons within the CustomDrawCell event in exactly the same manner as the XtraGrid does KB article for more information.
References:
Draw custom expand/collapse button in GridView Row
Custom Draw +/- button for Master Detail GridView
Grid - How to change the master-detail expand button
XtraGrid:Adding a button to a cell that will allow cell data to expand - collapse.