There are a couple of things wrong with your code.
Firstly, dictionaries have no fixed order, so the keys won't necessarily end up in the same order that they were inserted in:
>>> items = {
... 'Maya Executable': '',
... 'Render': '',
... 'Mayapy Interpreter': '',
... 'imgcvt': '',
... 'IMConvert': '',
... }
>>> items.keys()
['Mayapy Interpreter', 'IMConvert', 'imgcvt', 'Render', 'Maya Executable']
So "Maya Executable" isn't the first item in the list of keys.
Secondly, you are trying to set the current index before adding the items, when you should be setting it afterwards. As it is, the combo-box will just default to showing the first item, which would be "Mayapy Interpreter".
EDIT:
If you use an OrderedDict, your example code should work as expected:
from collections import OrderedDict
...
self.items = OrderedDict([
('Maya Executable', ''),
('Render', ''),
('Mayapy Interpreter', ''),
('imgcvt', ''),
('IMConvert', ''),
])
self.appExeCB.addItems(self.items.keys())
(NB: Python >= 2.7 is required for OrderedDict)