What do you do when you discover on a Friday evening that trips you want to book for train travel in Italy before departure on Monday are not available as E-Tickets via Rail Europe and that paper tickets (such a thing still exists) would not be sent until Monday?
You try Trenitalia site in English.
I have to say I did not have that problem when i booked my Paris-Toulouse train trip via SNCF.com last summer from Copenhagen.
On a positive note the Mini fares offered by Trenitalia start at 9 Euros and for travel midday from Rome to Venice on June 15, they have tickets available for 29 Euros, great price.
What's left to do?
Keep trying until a working solution pops up.