Accept your current offer at UNSW. If you get a new offer (see below), you can then later withdraw from UNSW.
Change your first pref to BE/BSc.
Firstly, please note that just because there is not a V next to a certain course, this does not mean that offers are NOT made in that course in the 2nd round. A V guarantees offers will be made (assuming there are applicants who meet the minimum cut off). If there is no V, then they "might" make offers depending on how many people accept next week.
For combined degrees at Sydney, you need both the generic BE/BSc ATAR (90.25) and the ATAR for the stream of engineering you want to do. Hence to do BE(Biomed)/BSc you also need to have ATAR > 90 (whic is automatic), but to do BE Mech Space with Science you need 99.8.
Do not worry about the timetable. If you get an offer to Sydney in the 2nd round you enrol in early Feb. Timetables for all students come out in mid/late Feb. In most cases USyd does not have caps on students in subejects (or first in best dressed).
I was debating between chem eng at unsw and biomed eng at usyd and in the end I put down chem eng as my first preference. I got accepted but after talking to uni people of both said courses, I found biomed eng was more of what I wanted (I couldn't do this any earlier as I was overseas and did not come back till preferences were over. Although biomed eng at usyd has no vacancies, b eng/b science has vacancies so would i be able to do b biomed eng/b science? My atar is well over the cut off. Also as I will be enrolling and organising my time table at a later date than those who got the main round offer, will there still be much choice left in the classes I want to do and my timetable?