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You can format the shading for subtotals separately from grand totals using the Format->Shading->Total section, but this will only give you one color per subtotal, and doesn't let you customize the text. You can change the text from "Total" to something else in the Format window->click on the Fields drop-down->choose the field->Header tab->totals section, but this only gives on value per total. The Basic Shading worksheet in the attached has that set up.
See the attached for a solution that at least gets you custom Total headers. I used duplicated data via custom SQL as well as custom fields to create the format. the methods are outlined in http://drawingwithnumbers.artisart.org/customizing-grand-totals-part-3/ and http://drawingwithnumbers.artisart.org/customizing-grand-totals-part-2/. You weren't clear about how much formatting you wanted to do on the headers vs. the data. Header formatting is pretty limited, for example you can't arbitrarily set some members of a dimension to be in bold and some normal weight, and you've already run into limitations of banding. In terms of columns, you can do stuff with size and color, but not font weight, I played with both in the attached. If you want to get really custom for that, you can use a multiple axis crosstab with dual axes for a column, the technique is outlined in http://public.tableausoftware.com/views/conditionalformattingv4/Introduction. If you were willing to limit yourself to having a fixed column size for both the header and the values, you could create an additional axis that would have the totals and then you could individually color the subtotals and totals.