I guess for the first item, you'd have to requery the list the form submits to in order to find out if there is anything already in the list for a given tester id and schedule. Then you could mark the current request as cancelled (if that is what you are trying to do?)
For the second item, you should be able to just create a validation formula - but put the start and end times on your form as calculated values with the formatting set to show you the XML value - so you know what the actual values are and can write the formulas accordingly.