Sorry you can't do that yet. In fact even if you use writecell() on an existing workbook that is nicely formatted with cell colors, underlines, fonts, borders, etc., it will blow away all your existing formatting. I informed them of this bug a long time ago and they said it's behaving as designed. I told them their design was terrible and it would force people to remain using xlswrite(), which they deprecated but at least that function does not blow away formatting when writing to an existing workbook.
Please, please, please call them on the phone or send a message to support@mathwork.com and tell them to fix writecell() so it doesn't remove formatting.
Until then your only choice is to continue to use xlswrite(), or use writecell() but then, if using Windows, you'll have to use ActiveX to format it exactly like you want. The xlswrite() option is easier than the ActiveX option but if you want the ActiveX option, see attached Excel class.