Hi,
The default country/state are stored in the address custom field.
Please edit your address custom fields in the HikaShop backend and change the "default value" then re-save the custom field.
About the UPS configuration, be sure that your products have weight configured.
The plugin lists all products with a weight in the cart and uses this product for his webservice call to UPS.
UPS requires a total weight in order to give you a shipping price (and with dimensions, it is better).
If there is no weight, UPS won't be called because the order weight will be null.
After that, be sure that the Joomla messages are right displayed in your website. You might have a UPS error message if there is a problem, like I had with my little test in the demo website:
Regards,
Jerome - Obsidev.com
HikaMarket & HikaSerial developer / HikaShop core dev team.
Also helping the HikaShop support team when having some time or couldn't sleep.
By the way, do not send me private message, use the "contact us" form instead.