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Say your current CTC is 5 LPA, and you apply to a tier 1 firm, will they think this is too low, maybe he's not worth it?

Do HRs do this while screening?
In house jobs they do. Your offer would most likely be 30% above your current ctc.
Na bro. They have their own pay bands, ultimately comes down to what you bring to the table and how much you can push up your numbers.

They might try to give you the lower end of the band, for instance if you make 45k right now but you know tech law and have done SEBI matters (just generally listing some niche works), they may bump you all the way up to 1.3L which should knock your socks off, except that band you're hired for might start at 1.3L and go till 1.6L.

Do your research, don't seem needy for the job, and know your shit. That's all.
I had a similar CTC before joining a tier 1 firm. It doesn't really matter much.
Related question: How does one go about switching from 4-6LPA firms to T1 firms?
Every single tier one firm is desperately looking for people who have got some form of training and will not make fresher-like mistakes with simple tasks. You may not be able to join at the same level as your contemporaries who have been working at T1 firms throughout, but within a few years, it won't matter. Approach the HRs, either by yourself or through someone who may already know who's been working in the firm.