OK, first. reportable income (work and SS retirement) is 39K. std ded got all Fed/St w/h back. But pd nearly 20k in maint for 2013 div. should I itemize?

Standard Deduction.  If the $20K you paid is classified as alimony, then yes I would report it.  But alimony is an adjustment to income so you will still be taking the standard deduction. In TurboTax, go to the search at the top of the page then enter alimony paid.  You will get a Jump To function to take you to the screens to enter the payments and your ex spouse's social security number.  She will need to report as income on her return.

Here is some information on reporting Alimony in TurboTax

Payments are alimony if all the following are true.

• Payments are required by a divorce or separation instrument.
• Payer and recipient spouse do not file a joint return.
• Payment is in cash (including checks and money orders).
• Payments not considered to be in cash include noncash property settlements, spouse’s part of community income, and upkeep for the payer’s property, and use of the payer’s property.
• Payment is not designated in the instrument as “not alimony.”
• Divorced and legally separated spouses are not members of the same household when payment is made.
• Payments are not required after death of the recipient spouse.2•Payment is not treated as child support