You will pay full tax, PRSI and USC on the pay-in-lieu of holidays with your old employer. This is unfortunate but there is nothing I am aware of that can change the tax and other deductions. It's treated as a once-off taxable payment to you. If you take unpaid holidays in your new job, assuming your are not being taxed on an emergency or week 1 basis, your deductions should automatically reduce as your pay does. The calculations are done on a YTD basis. Using basic assumptions, it should be possible for your own payroll department to see what the extra payments followed by the reduced payments will mean for you financially.
In summary will you have a big payday with higher tax and other deductions on leaving the current job, followed by smaller pay-days with small payments and smaller deductions (or even refunds) when you take leave, All other thinks being equal, your year-end deductions should balance out, but sit down with someone and do your own P21 end-of-year balancing statement to see. HTH